TWI712623B - Fluorine-containing acrylic composition and its manufacturing method, fluorine-containing active energy ray curable composition and article - Google Patents
Fluorine-containing acrylic composition and its manufacturing method, fluorine-containing active energy ray curable composition and article Download PDFInfo
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- TWI712623B TWI712623B TW106110586A TW106110586A TWI712623B TW I712623 B TWI712623 B TW I712623B TW 106110586 A TW106110586 A TW 106110586A TW 106110586 A TW106110586 A TW 106110586A TW I712623 B TWI712623 B TW I712623B
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- fluorine
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- 239000000203 mixture Substances 0.000 title claims abstract description 145
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 133
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000011737 fluorine Substances 0.000 title claims abstract description 99
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- -1 Fluorinated acrylic compound Chemical class 0.000 claims abstract description 144
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 37
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 31
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 25
- 125000000962 organic group Chemical group 0.000 claims abstract description 15
- 125000005647 linker group Chemical group 0.000 claims abstract description 14
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 36
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- 239000007788 liquid Substances 0.000 abstract description 24
- 230000003373 anti-fouling effect Effects 0.000 abstract description 20
- 239000000758 substrate Substances 0.000 abstract description 15
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000001568 sexual effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000000576 coating method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 0 CCC(C)(C)N* Chemical compound CCC(C)(C)N* 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 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 5
- 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 5
- LGSZVMFFSUHPPX-UHFFFAOYSA-N C(C(C)OCCN=C=O)N=C=O Chemical compound C(C(C)OCCN=C=O)N=C=O LGSZVMFFSUHPPX-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 4
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229940070765 laurate Drugs 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 2
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TYCFGHUTYSLISP-UHFFFAOYSA-N 2-fluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C TYCFGHUTYSLISP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/702—Isocyanates or isothiocyanates containing compounds having carbon-to-carbon double bonds; Telomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本發明的課題為提供一種不增加不具有與丙烯醯基反應之基的揮發性有機化合物且可賦予撥液性、防污性之含氟丙烯酸組成物、其製法、該含氟活性能量線硬化性組成物、及於基材表面具有此硬化物層之物品。 The subject of the present invention is to provide a fluorine-containing acrylic composition that can impart liquid repellency and antifouling properties without increasing volatile organic compounds that do not have a group reactive with acryloyl groups, its preparation method, and curing of the fluorine-containing active energy rays Sexual composition, and articles with this hardened layer on the surface of the substrate.
作為本發明的解決手段,係提供一種含氟丙烯酸組成物,其係含有(A)及(B), As a solution of the present invention, a fluorine-containing acrylic composition is provided, which contains (A) and (B),
(A)下式之含氟丙烯酸化合物、X-Rf1-Z1-Q1-[Z2OR1]a (A) Fluorinated acrylic compound of the following formula, X-Rf 1 -Z 1 -Q 1 -[Z 2 OR 1 ] a
(Rf1為2價全氟聚醚基,Q1為含有Si之(a+1)價連接基,Z1為2價連接基,Z2為2價烴基,R1為H、或含有(α取代)丙烯醯基之1價有機基,X為氟原子或-Z1-Q1-[Z2OR1]a之基;a為1~10) (Rf 1 is a divalent perfluoropolyether group, Q 1 is a (a+1) valent linking group containing Si, Z 1 is a divalent linking group, Z 2 is a divalent hydrocarbon group, R 1 is H, or contains ( α substituted) a monovalent organic group of acryloyl group, X is a fluorine atom or a group of -Z 1 -Q 1 -[Z 2 OR 1 ] a ; a is 1~10)
(B)25℃之黏度為100mPa.s以下,且包含(甲基)丙烯醯基之丙烯酸化合物 (B) The viscosity at 25°C is 100mPa. s or less, and containing (meth)acrylic acid compound
此等之質量比為0.03<(A)/(B)<10,且未摻合不具有與丙烯醯基反應之基的揮發性有機化合物。 The mass ratio of these is 0.03<(A)/(B)<10, and volatile organic compounds that do not have groups that react with acryl groups are not blended.
Description
本發明係關於藉由添加在紫外線或電子束等之活性能量線硬化性組成物,可賦予撥液性、防污性之含氟丙烯酸組成物、及該含氟丙烯酸組成物之製造方法、具有該組成物之含氟活性能量線硬化性組成物、以及於基材表面具有此組成物之硬化物層的物品。 The present invention relates to a fluorine-containing acrylic composition that can impart liquid repellency and antifouling properties by adding an active energy ray curable composition such as ultraviolet rays or electron beams, and a method for producing the fluorine-containing acrylic composition. The fluorine-containing active energy ray curable composition of the composition, and an article having a hardened layer of the composition on the surface of the substrate.
以往,作為保護樹脂成形體等之表面的手段,一般廣泛使用硬塗處理。此係於成形體的表面形成硬質的硬化樹脂層(硬塗層),難以劃傷者。作為構成硬塗層之材料,大量使用藉由熱硬化性樹脂或紫外線或電子束硬化型樹脂等活性能量線之硬化性組成物。 In the past, as a means for protecting the surface of a resin molded body, etc., a hard coat treatment has been widely used. This is to form a hard hardened resin layer (hard coat layer) on the surface of the molded body, making it difficult to scratch the person. As the material constituting the hard coat layer, a large amount of curable composition using active energy rays such as thermosetting resin or ultraviolet or electron beam curable resin is used.
另外,伴隨樹脂成形品之利用領域的擴大或高加成價值化的流動,已提高對於硬化樹脂層(硬塗層)之高機能化的要求,作為其之一,係尋求對硬塗層之防污性的賦予。此係藉由於硬塗層的表面賦予撥水性、撥油性等之性質,可成為難以污染,或即使污染亦可輕易去除者。 In addition, with the expansion of the application field of resin molded products or the flow of high added value, the demand for high performance of the hardened resin layer (hard coat) has been increased. As one of these, the demand for hard coat Grant of antifouling properties. This is because the surface of the hard coat layer imparts water repellency, oil repellency, etc., which can be difficult to contaminate or can be easily removed even if contaminated.
作為對硬塗層賦予防污性之方法,雖廣泛使 用於一旦形成之硬塗層表面塗佈及/或定著含氟防污劑之方法,但針對將含氟硬化性成分添加在硬化前之硬化樹脂組成物,藉由將此塗佈硬化,同時進行硬塗層的形成與防污性的賦予之方法亦已進行研究。例如,日本特開平6-211945號公報(專利文獻1)中,顯示有藉由於丙烯酸系之硬化性樹脂組成物添加氟烷基丙烯酸酯使其硬化,製造賦予防污性之硬塗層。 As a method of imparting antifouling properties to hard coats, although widely used It is used for the method of coating and/or fixing the fluorine-containing antifouling agent on the surface of the hard coat layer once formed, but for the hardened resin composition before hardening by adding the hardenable fluorine component, by coating and hardening, The method of simultaneously forming a hard coat layer and imparting antifouling properties has also been studied. For example, in Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1), it is shown that a hard coat layer with antifouling properties is produced by adding a fluoroalkyl acrylate to an acrylic curable resin composition.
另外,硬塗處理為了提昇其塗佈性或被膜性能,於藉由有機溶劑稀釋之塗佈液的操作已被廣泛執行。惟,近年來從對環境或人體影響的懸念,已提高抑制揮發性有機溶劑等之揮發性有機化合物(VOC)的使用之動作,針對硬塗之塗佈液亦強烈要求高固體化或無溶劑化。伴隨此,針對為了對如前述之硬塗的塗佈液賦予撥液性、防污性而添加之添加劑組成物,亦正追求未包含無揮發性有機溶劑等之反應性基之揮發性有機化合物的組成者。 In addition, in order to improve the coatability or film performance of the hard coating process, the operation of the coating liquid diluted with an organic solvent has been widely performed. However, in recent years, from the suspense of the impact on the environment or the human body, the action to suppress the use of volatile organic solvents (VOC) has been improved, and the coating liquid for hard coating is also strongly required to be highly solid or solvent-free化. Along with this, for the additive composition added to impart liquid repellency and antifouling properties to the aforementioned hard-coated coating liquid, there is also a pursuit of volatile organic compounds that do not contain reactive groups such as volatile organic solvents. The constituents.
[專利文獻1]日本特開平6-211945號公報 [Patent Document 1] Japanese Patent Application Publication No. 6-211945
[專利文獻2]日本特開2010-53114號公報 [Patent Document 2] JP 2010-53114 A
[專利文獻3]日本特開2010-138112號公報 [Patent Document 3] JP 2010-138112 A
[專利文獻4]日本特開2010-285501號公報 [Patent Document 4] JP 2010-285501 A
本發明係鑑於上述事情而完成者,藉由抑制無反應性基之揮發性有機化合物的含量,提供一種添加在硬化性組成物時,不增加作為硬化性組成物全體之不具有與丙烯醯基反應之基的(非反應性之)揮發性有機化合物(尤其是於分子中未含有(甲基)丙烯醯基之非反應性的揮發性有機化合物),且可賦予撥液性、防污性之含氟丙烯酸組成物、及該含氟丙烯酸組成物之製造方法、具有該組成物之含氟活性能量線硬化性組成物、以及於基材表面具有此組成物的硬化物層之物品作為目的。 The present invention has been completed in view of the foregoing. By suppressing the content of non-reactive groups of volatile organic compounds, it provides a curable composition that does not increase the curable composition that does not have an acrylic acid group. Reactive (non-reactive) volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups in the molecule), and can impart liquid repellency and antifouling properties The fluorine-containing acrylic composition, the manufacturing method of the fluorine-containing acrylic composition, the fluorine-containing active energy ray curable composition having the composition, and the article having the hardened layer of the composition on the surface of the substrate are intended .
本發明者作為可對如此之硬化性樹脂組成物賦予防污性之氟化合物,已進行各式各樣的開發,例如提案有日本特開2010-53114號公報(專利文獻2)、日本特開2010-138112號公報(專利文獻3)、日本特開2010-285501號公報(專利文獻4)等所示之可光硬化的氟化合物。 The inventors of the present invention have made various developments as fluorine compounds that can impart antifouling properties to such curable resin compositions. For example, Japanese Patent Application Publication No. 2010-53114 (Patent Document 2) and Japanese Patent Application Publication No. 2010-53114 have been proposed. Photocurable fluorine compounds shown in 2010-138112 (Patent Document 3) and JP 2010-285501 A (Patent Document 4).
此等藉由於1分子中具有氟聚醚構造與複數丙烯醯基之構造,雖可對硬化性樹脂組成物賦予高防污性,但另一方面,由於於單體是難以操作之高黏稠液體,為了容易操作,提高與樹脂組成物的混合性,故有必要作為以高揮發性之有機溶劑稀釋的溶液操作。因此有無法直接摻合在無溶劑型之硬塗劑或塗料的問題。 These structures have a fluoropolyether structure and a plurality of acryl groups in one molecule, although high antifouling properties can be imparted to the curable resin composition, but on the other hand, because the monomer is a highly viscous liquid that is difficult to handle In order to facilitate handling and improve the compatibility with the resin composition, it is necessary to operate as a solution diluted with a highly volatile organic solvent. Therefore, there is a problem that it cannot be directly blended with solvent-free hard coat agents or paints.
因此,本發明者努力進一步研究的結果,發 現一種含氟丙烯酸組成物,其係包含(A)後述之式(1)表示之含氟丙烯酸化合物、與(B)在25℃之黏度為100mPa.s以下,且於1分子中包含1個或2個(甲基)丙烯醯基之丙烯酸化合物,其特徵為(A)成分與(B)成分的質量比為0.03<(A)/(B)<10的範圍內,未摻合不具有與丙烯醯基反應之基的揮發性有機化合物(尤其是於分子中未含有(甲基)丙烯醯基之非反應性的揮發性有機化合物),藉由將該含氟丙烯酸組成物添加在活性能量線硬化性組成物,可得到具有撥液性、防污性,尚且抑制揮發性有機化合物的含量之含氟活性能量線硬化性組成物,而終至完成本發明。 Therefore, as a result of further research, the inventors found There is a fluorine-containing acrylic composition, which contains (A) the fluorine-containing acrylic compound represented by the formula (1) described later, and (B) the viscosity at 25° C. is 100 mPa. s or less, an acrylic compound containing one or two (meth)acrylic groups in a molecule, characterized in that the mass ratio of (A) component to (B) component is 0.03<(A)/(B) Within the range of <10, no volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups) that do not have groups reactive with acryloyl groups are incorporated in the molecule, by By adding the fluorine-containing acrylic composition to the active energy ray curable composition, a fluorine-containing active energy ray curable composition having liquid repellency and antifouling properties while suppressing the content of volatile organic compounds can be obtained. To complete the present invention.
據此,本發明係提供下述之含氟丙烯酸組成物及其製造方法等。 Accordingly, the present invention provides the following fluorine-containing acrylic composition and its manufacturing method.
[1]一種含氟丙烯酸組成物,其係含有下述之(A)及(B)作為必須成分, [1] A fluorine-containing acrylic composition containing the following (A) and (B) as essential components,
(A)下述一般式(1)表示之含氟丙烯酸化合物,X-Rf1-Z1-Q1-[Z2OR1]a (1) (A) The fluorine-containing acrylic compound represented by the following general formula (1), X-Rf 1 -Z 1 -Q 1 -[Z 2 OR 1 ] a (1)
(式中,Rf1係藉由碳數1~6之全氟伸烷基與氧原子而構成之分子量800~20,000之2價全氟聚醚基,Q1係獨立至少包含(a+1)個矽原子之(a+1)價連接基,可成為環狀構造,可包含選自氧原子、氮原子及氟原子中之至少1種;Z1獨立為碳數1~20之亦可包含選自氧原子、氮原子及矽原子中之至少1種的2價連接基,途中可包含環狀構造,可成為分支,一部分的氫原子可被氟原子取代;Z2獨立為碳數1~200之亦可包含選自氧原子、氮原子及矽原子中之至 少1種的2價烴基,途中可包含環狀構造;R1獨立為氫原子、或含有:亦可包含選自氧原子及氮原子中之至少1種的丙烯醯基或α取代丙烯醯基之1價有機基,惟,R1係平均於1分子中至少具有1個含有前述丙烯醯基或α取代丙烯醯基之1價有機基;X為氟原子或-Z1-Q1-[Z2OR1]a表示之1價基;a為1~10之整數) (In the formula, Rf 1 is a divalent perfluoropolyether group with a molecular weight of 800 to 20,000 formed by a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom, and Q 1 independently contains at least (a+1) The (a+1) valence linking group of one silicon atom can be a cyclic structure and can contain at least one selected from oxygen atom, nitrogen atom and fluorine atom; Z 1 is independently of carbon number 1-20 and can also be included A divalent linking group selected from at least one of oxygen atoms, nitrogen atoms and silicon atoms, which may contain a cyclic structure in the way, may become branched, and some of the hydrogen atoms may be substituted by fluorine atoms; Z 2 is independently a carbon number of 1~ 200 may also include at least one divalent hydrocarbon group selected from oxygen atoms, nitrogen atoms and silicon atoms, and may include a cyclic structure in the way; R 1 is independently a hydrogen atom, or contains: may also include oxygen atoms and At least one of the nitrogen atoms is a monovalent organic group of an acryloyl group or an α-substituted acryloyl group. However, R 1 is an average of at least one containing the aforementioned acryloyl group or an α-substituted acryloyl group in one molecule. A valent organic group; X is a fluorine atom or -Z 1 -Q 1 -[Z 2 OR 1 ] a monovalent group represented by a; a is an integer from 1 to 10)
(B)在25℃之黏度為100mPa.s以下,且於1分子中包含1個或2個(甲基)丙烯醯基之丙烯酸化合物 (B) The viscosity at 25°C is 100mPa. s or less, and contains 1 or 2 (meth)acrylic acid compounds in one molecule
(A)成分與(B)成分的質量比為0.03<(A)/(B)<10的範圍內,尚且,係未摻合不具有與丙烯醯基反應之基的揮發性有機化合物者。 The mass ratio of the component (A) to the component (B) is in the range of 0.03<(A)/(B)<10, and moreover, it is not blended with a volatile organic compound that does not have a group reactive with an acryloyl group.
[2]如[1]之含氟丙烯酸組成物,其中,作為(B)成分的一部分或全部,係包含下述一般式(2)表示之丙烯酸化合物,CH2=CR6COOR5 (2) [2] The fluorine-containing acrylic composition according to [1], wherein, as part or all of component (B), it contains an acrylic compound represented by the following general formula (2), CH 2 =CR 6 COOR 5 (2)
(式中,R5為碳數1~20之烷基、芳基或芳烷基,可為分支亦可為環狀,可包含脂肪族不飽和鍵、胺基甲酸乙酯鍵、醚鍵、異氰酸酯基、羥基;R6為氫原子或甲基、氟原子、碳數1~6之氟烷基)。 (In the formula, R 5 is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain aliphatic unsaturated bonds, urethane bonds, ether bonds, Isocyanate group, hydroxyl group; R 6 is a hydrogen atom or a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms).
[3]如[1]或[2]之含氟丙烯酸組成物,其中,作為(B)成分,係包含氫原子的一部分被選自F、Cl、及Br中之鹵素原子取代之丙烯酸化合物。 [3] The fluorine-containing acrylic composition according to [1] or [2], wherein the component (B) is an acrylic compound in which a part of hydrogen atoms is substituted with a halogen atom selected from F, Cl, and Br.
[4]如[3]之含氟丙烯酸組成物,其中,作為(B)成分的一部分或全部,係包含下述一般式(3)表示之含氟丙烯 酸化合物,CH2=CR2COOZ3Rf2 (3) [4] The fluorine-containing acrylic composition according to [3], wherein, as part or all of component (B), it contains a fluorine-containing acrylic compound represented by the following general formula (3), CH 2 =CR 2 COOZ 3 Rf 2 (3)
(惟,式中,R2係獨立為氫原子、F、Cl、Br或碳數1~8之1價烴基,烴基中之氫原子可被F、Cl、Br取代;Z3係獨立為碳數1~8之2價烴基,可成為分支,可於途中包含氧原子、羥基;Rf2為氟原子數2~20之氟烷基,可包含氫原子、氧原子,可成為分支)。 (However, in the formula, R 2 is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be replaced by F, Cl, Br; Z 3 is independently a carbon A divalent hydrocarbon group of 1 to 8 can be branched, and it can contain an oxygen atom and a hydroxyl group in the middle; Rf 2 is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain a hydrogen atom and an oxygen atom, and can be branched).
[5]如[1]~[4]中任一項之含氟丙烯酸組成物,其中,在(A)成分之一般式(1)表示之含氟丙烯酸化合物,Rf1為以下3種類之構造式表示之2價全氟聚醚基中之任一個,-CF2O-(CF2O)p(CF2CF2O)q-CF2- [5] The fluorine-containing acrylic composition according to any one of [1] to [4], wherein, in the fluorine-containing acrylic compound represented by the general formula (1) of component (A), Rf 1 is the following 3 types of structures Any one of the bivalent perfluoropolyether groups represented by the formula, -CF 2 O-(CF 2 O) p (CF 2 CF 2 O) q -CF 2-
(惟,( )所包括之重複單位的配列為無規,p為1~200之整數,q為1~170之整數,p+q為6~201;s為0~6之整數,t、u分別為1~100之整數,t+u為2~120之整數;v為1~120之整數)。 (However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120; v is an integer from 1 to 120).
[6]如[1]~[5]中任一項之含氟丙烯酸組成物,其中,在(A)成分,一般式(1)中之Z1為下述式表示之任一種構造,-CH2CH2CH2CH2- [6] The fluorinated acrylic composition according to any one of [1] to [5], wherein, in the component (A), Z 1 in the general formula (1) is any structure represented by the following formula,- CH 2 CH 2 CH 2 CH 2-
-CH2OCH2CH2CH2- -CH 2 OCH 2 CH 2 CH 2-
[7]如[1]~[6]中任一項之含氟丙烯酸組成物,其中在(A)成分,一般式(1)中之Q1為下述式表示之構造,
(式中,a係獨立為1~10之整數)。 (In the formula, a is an integer from 1 to 10 independently).
[8]如[1]~[7]中任一項之含氟丙烯酸組成物,其中,(A)成分係選自下述式表示之含氟丙烯酸化合物,
(式中,Rf’為-CF2O(CF2O)p(CF2CF2O)qCF2-,p為1~200之整數,q為1~170之整數,p+q為6~201;e1為1~30之整數;R’為氫原子、
或
此等可混在於一個分子中;惟,R’係平均於1分子中至少含有1個上述(甲基)丙烯醯基之1價有機基,v1為2~120之整數)。 These can be mixed in one molecule; however, R'contains at least one monovalent organic group of the (meth)acryloyl group in one molecule on average, and v1 is an integer of 2 to 120).
[9]一種含氟丙烯酸組成物之製造方法,其特徵為具有在(B)的存在下,使(C)與(D)進行反應,而生成(A)之步驟,(B)在25℃之黏度為100mPa.s以下,且於1分子中包含1個或2個(甲基)丙烯醯基之丙烯酸化合物;(C)下述一般式(4)表示之含氟多官能醇化合物;X1-Rf1-Z1-Q1-[Z2OH]a (4) [9] A method for producing a fluorine-containing acrylic composition, characterized by having a step of reacting (C) and (D) in the presence of (B) to produce (A), (B) at 25°C The viscosity is 100mPa. s or less, and an acrylic compound containing one or two (meth)acryloyl groups in one molecule; (C) a fluorine-containing polyfunctional alcohol compound represented by the following general formula (4); X 1 -Rf 1- Z 1 -Q 1 -[Z 2 OH] a (4)
(式中,X1為氟原子或-Z1-Q1-[Z2OH]a表示之基,Rf1藉由碳數1~6之全氟伸烷基與氧原子而構成之分子量800~20,000之2價全氟聚醚基,Z1獨立為碳數1~20之亦可包含選自氧原子、氮原子及矽原子中之至少1種的2價連接基,Q1係獨立至少包含(a+1)個矽原子之(a+1)價連接基,可成為環狀構造,可包含選自氧原子、氮原子及氟原子中之至少1種;Z2獨立為碳數1~200之亦可包含選自氧原子、氮原子及矽原子中之至少1種的2價烴基,途中可包含 環狀構造;a為1~10之整數);(D)於1分子中具有一個異氰酸酯基與至少一個(甲基)丙烯醯基之化合物;(A)下述一般式(1)表示之含氟丙烯酸化合物X-Rf1-Z1-Q1-[Z2OR1]a (1) (In the formula, X 1 is a fluorine atom or a group represented by -Z 1 -Q 1 -[Z 2 OH] a , Rf 1 is composed of a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom with a molecular weight of 800 ~20,000 divalent perfluoropolyether group, Z 1 is independently a divalent linking group with 1-20 carbon atoms, which may also contain at least one selected from oxygen atom, nitrogen atom and silicon atom, Q 1 is independently at least The (a+1) valent linking group containing (a+1) silicon atoms can be a cyclic structure and can contain at least one selected from the group consisting of oxygen atoms, nitrogen atoms and fluorine atoms; Z 2 is independently carbon number 1. ~200 can also contain at least one divalent hydrocarbon group selected from oxygen atoms, nitrogen atoms and silicon atoms, and can contain a cyclic structure on the way; a is an integer from 1 to 10); (D) has in 1 molecule A compound of one isocyanate group and at least one (meth)acryloyl group; (A) the fluorinated acrylic compound represented by the following general formula (1) X-Rf 1 -Z 1 -Q 1 -[Z 2 OR 1 ] a (1)
(式中,Rf1、Z1、Q1、Z2、a係與上述相同;R1係獨立為氫原子、或含有:亦可包含選自氧原子及氮原子中之至少1種的丙烯醯基或α取代丙烯醯基之1價有機基,惟,R1係平均於1分子中至少具有1個含有前述丙烯醯基或α取代丙烯醯基之1價有機基,X為氟原子或-Z1-Q1-[Z2OR1]a表示之1價基) (In the formula, Rf 1 , Z 1 , Q 1 , Z 2 , and a are the same as above; R 1 is independently a hydrogen atom, or contains: Propylene which may contain at least one selected from an oxygen atom and a nitrogen atom The monovalent organic group of an acyl group or an α-substituted acryloyl group, however, R 1 is an average of at least one monovalent organic group containing the aforementioned acryloyl group or an α-substituted acryloyl group in one molecule, and X is a fluorine atom or -Z 1 -Q 1 -[Z 2 OR 1 ] a represents the monovalent base)
上述(A)成分與(B)成分的質量比為0.03<(A)/(B)<10的範圍內,尚且,得到未摻合不具有與丙烯醯基反應之基的揮發性有機化合物之含氟丙烯酸組成物。 The mass ratio of the above-mentioned (A) component and (B) component is within the range of 0.03<(A)/(B)<10. Moreover, it is obtained without blending of volatile organic compounds that do not have groups reactive with acryloyl groups Fluorinated acrylic composition.
[10]如[9]之含氟丙烯酸組成物之製造方法,其中,作為(B)成分的一部分或全部,係包含下述一般式(2)表示之丙烯酸化合物及/或下述一般式(3)表示之含氟丙烯酸化合物,CH2=CR6COOR5 (2) [10] The method for producing a fluorine-containing acrylic composition according to [9], wherein part or all of component (B) contains an acrylic compound represented by the following general formula (2) and/or the following general formula ( 3) Fluorinated acrylic compound represented, CH 2 =CR 6 COOR 5 (2)
(式中,R5為碳數1~20之烷基、芳基或芳烷基,可為分支亦可為環狀,可包含脂肪族不飽和鍵、胺基甲酸乙酯鍵、醚鍵、異氰酸酯基、羥基;R6為氫原子或甲基、氟原子、碳數1~6之氟烷基) (In the formula, R 5 is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain aliphatic unsaturated bonds, urethane bonds, ether bonds, Isocyanate group, hydroxyl group; R 6 is a hydrogen atom or a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms)
CH2=CR2COOZ3Rf2 (3) CH 2 =CR 2 COOZ 3 Rf 2 (3)
(惟,式中,R2係獨立為氫原子、F、Cl、Br或碳數1~8之1價烴基,烴基中之氫原子可被F、Cl、Br取代;Z3係獨立為碳數1~8之2價烴基,可成為分支,可於途中包含氧原子、羥基;Rf2為氟原子數2~20之氟烷基,可包含氫原子、氧原子,亦可為分支) (However, in the formula, R 2 is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be replaced by F, Cl, Br; Z 3 is independently a carbon A divalent hydrocarbon group of 1 to 8 can be branched, and it can contain an oxygen atom and a hydroxyl group in the middle; Rf 2 is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain a hydrogen atom, an oxygen atom, or it can be branched)
在(C)成分之一般式(4)及(A)成分之一般式(1),Rf1為以下3種類構造式表示之2價全氟聚醚基中之任一者,-CF2O-(CF2O)p(CF2CF2O)q-CF2- In the general formula (4) of component (C) and general formula (1) of component (A), Rf 1 is any one of the divalent perfluoropolyether groups represented by the following three structural formulas, -CF 2 O -(CF 2 O) p (CF 2 CF 2 O) q -CF 2-
(惟,( )所包括之重複單位的配列為無規,p為1~200之整數,q為1~170之整數,p+q為6~201;s為0~6之整數,t、u分別為1~100之整數,t+u為2~120之整數;v為1~120之整數) (However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120; v is an integer from 1 to 120)
Z1為下述式表示之任一種構造,-CH2CH2CH2CH2- Z 1 is any structure represented by the following formula, -CH 2 CH 2 CH 2 CH 2-
-CH2OCH2CH2CH2- -CH 2 OCH 2 CH 2 CH 2-
Q1為下述式表示之構造,
(式中,a係獨立為1~10之整數)。 (In the formula, a is an integer from 1 to 10 independently).
[11]一種含氟活性能量線硬化性組成物,其特徵為相對於活性能量線硬化性組成物(E)100質量份,包含0.005~40質量份之如[1]~[8]中任一項之含氟丙烯酸組成物。 [11] A fluorine-containing active energy ray curable composition characterized by containing 0.005 to 40 parts by mass of any of [1] to [8] relative to 100 parts by mass of the active energy ray curable composition (E) One item of fluorine-containing acrylic composition.
[12]如[11]之含氟活性能量線硬化性組成物,其中,活性能量線硬化性組成物(E)係含有(Ea)丙烯酸化合物:100質量份、(Eb)光聚合起始劑:0.1~15質量份而成。 [12] The fluorine-containing active energy ray curable composition according to [11], wherein the active energy ray curable composition (E) contains (Ea) acrylic compound: 100 parts by mass, (Eb) photopolymerization initiator : 0.1-15 parts by mass.
[13]一種物品,其係於表面具有如[11]或[12]之含氟活性能量線硬化性組成物的硬化物層。 [13] An article having a hardened layer of the fluorine-containing active energy ray hardenable composition such as [11] or [12] on the surface.
根據本發明之含氟丙烯酸組成物,可提供一種不增加不具有與丙烯醯基反應之基的揮發性有機化合物(尤其是於分子中未含有(甲基)丙烯醯基之非反應性的揮發性有機化合物)的含量添加在活性能量線硬化性組成物,且可賦予撥液性、防污性之含氟活性能量線硬化性組成物。 According to the fluorine-containing acrylic composition of the present invention, it is possible to provide a non-reactive volatile organic compound that does not have groups reactive with acryloyl groups (especially non-reactive volatile organic compounds that do not contain (meth)acryloyl groups in the molecule). The content of the organic compound) is added to the active energy ray curable composition, and can impart liquid repellency and antifouling properties to a fluorine-containing active energy ray curable composition.
本發明之含氟丙烯酸組成物,其係包含(A)後述之式(1)表示之含氟丙烯酸化合物、與(B)在25℃之黏度為100mPa.s以下,且於1分子中包含1個或2個(甲基)丙烯醯基之丙烯酸化合物,其特徵為(A)成分與(B)成分的質量比為0.03<(A)/(B)<10的範圍內,未摻合不具有與丙烯醯基反應之基的揮發性有機化合物(尤其是於分子中未含有(甲基)丙烯醯基之非反應性的揮發性有機化合物)。 The fluorine-containing acrylic composition of the present invention contains (A) the fluorine-containing acrylic compound represented by the formula (1) described later, and (B) the viscosity at 25° C. is 100 mPa. s or less, an acrylic compound containing one or two (meth)acrylic groups in a molecule, characterized in that the mass ratio of (A) component to (B) component is 0.03<(A)/(B) Within the range of <10, no volatile organic compound (especially non-reactive volatile organic compound that does not contain a (meth)acryloyl group) in the molecule is not blended with a group reactive with acryloyl group.
在本發明之含氟丙烯酸組成物的第一必須成分即(A)成分之含氟丙烯酸化合物係以下述一般式(1)表示。尚,在本發明,所謂「丙烯酸化合物」,係具有丙烯醯基、α取代丙烯醯基之化合物的總稱,亦包含於分子內具有胺基甲酸乙酯鍵之胺基甲酸乙酯丙烯酸酯類、或於各種聚合物的側鏈或末端以任意之方法導入2個以上丙烯醯基、α取代丙烯醯基之化合物。又,在本發明所謂「(甲 基)丙烯酸酯」,係表示丙烯酸酯與甲基丙烯酸酯的一者或兩者。 The fluorine-containing acrylic compound of component (A) which is the first essential component of the fluorine-containing acrylic composition of the present invention is represented by the following general formula (1). Furthermore, in the present invention, the so-called "acrylic compound" is a general term for compounds having acryloyl groups and α-substituted acryloyl groups, and also includes urethane acrylates having urethane bonds in the molecule, Or introduce 2 or more acryloyl and α-substituted acryloyl compounds into the side chains or ends of various polymers by any method. Also, in the present invention, the so-called "(甲 "Acrylate" means one or both of acrylate and methacrylate.
X-Rf1-Z1-Q1-[Z2OR1]a (1) X-Rf 1 -Z 1 -Q 1 -[Z 2 OR 1 ] a (1)
上述式(1)中,Rf1係藉由碳數1~6,尤其是1~4之全氟伸烷基與氧原子所構成之分子量800~20,000之2價全氟聚醚基。尤其是以分子量1,000~10,000之直鏈全氟聚醚基較佳。尚,在本發明,分子量係根據1H-NMR及19F-NMR從末端構造與主鏈構造的比率算出之數平均分子量。 In the above formula (1), Rf 1 is a divalent perfluoropolyether group with a molecular weight of 800 to 20,000 composed of a perfluoroalkylene group having 1 to 4 carbon atoms, especially 1 to 4, and an oxygen atom. In particular, a linear perfluoropolyether group with a molecular weight of 1,000 to 10,000 is preferred. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure and the main chain structure based on 1 H-NMR and 19 F-NMR.
作為Rf1,尤其是以由主要構造為以下所示之重複單位群組中之任一個或複數組合所構成者較佳。 As Rf 1 , it is particularly preferable to be composed of any one or plural combination of the repeating unit group shown below.
-CF2O- -CF 2 O-
-CF2CF2O- -CF 2 CF 2 O-
-CF2CF2CF2O- -CF 2 CF 2 CF 2 O-
-CF(CF3)CF2O- -CF(CF 3 )CF 2 O-
於此,作為不適於主要構造的部分,可列舉與Z1的鍵結部分、主鏈構造構築時之起始劑碎片或副生成構造。 Here, as a part that is not suitable for the main structure, the bonding part with Z 1 and the initiator fragment or by-product structure when the main chain structure is constructed can be cited.
其中,尤其是適合Rf1為以下中之任一個構造者。 Among them, it is particularly suitable that Rf 1 is any one of the following structures.
-CF2O-(CF2O)p(CF2CF2O)q-CF2- -CF 2 O-(CF 2 O) p (CF 2 CF 2 O) q -CF 2-
於此,p與q係表示( )所包括之-CF2O-構造與-CF2CF2O-構造之個別的總數,個別的-CF2O-構造與-CF2CF2O-構造的排列為無規。此時以p為1~200之整數,q為1~170之整數,p+q為6~201的整數較佳。 Thereto, P and q are diagrams () included in the structure of -CF 2 O- and -CF 2 CF 2 O- total configuration of the individual, the individual structure -CF 2 O- and -CF 2 CF 2 O- structure The arrangement is random. In this case, p is an integer from 1 to 200, q is an integer from 1 to 170, and p+q is an integer from 6 to 201.
又,以s為0~6之整數,t、u分別為1~100之整數,t+u為2~120之整數,v為1~120之整數較佳。 Furthermore, taking s as an integer from 0 to 6, t and u are respectively an integer from 1 to 100, t+u is an integer from 2 to 120, and v is preferably an integer from 1 to 120.
p+q、t+u或v之值小時,作為氟化合物所追求的特性難以出現,此等之值過大時,與其他成分的相溶性惡化。在組成物內之p、q及p+q、t、u及t+u或v之值可為單一亦可為具有分布,具有分布的情況下,以由19F-NMR等所尋求之數平均分子量滿足上述範圍較佳。 When the value of p+q, t+u, or v is small, the characteristics sought as a fluorine compound are unlikely to appear. When these values are too large, the compatibility with other components deteriorates. The values of p, q and p+q, t, u and t+u or v in the composition can be single or distributed. In the case of distribution, the value sought by 19 F-NMR etc. The average molecular weight preferably satisfies the above range.
上述式(1)中,Z1係獨立為碳數1~20之亦可包含選自氧原子、氮原子及矽原子中之至少1種的2價連接基,途中可包含環狀構造,可成為分支,一部分的氫原子可被氟原子取代。 In the above formula (1), Z 1 is independently a divalent linking group with 1 to 20 carbon atoms, which may also include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure on the way, Become a branch, part of the hydrogen atoms can be replaced by fluorine atoms.
作為Z1之較佳者,可列舉以下之構造。 As a preferable one of Z 1 , the following structures can be cited.
-CH2CH2- -CH 2 CH 2-
-CH2CH2CH2- -CH 2 CH 2 CH 2-
-CH2CH2CH2CH2- -CH 2 CH 2 CH 2 CH 2-
-CH2OCH2CH2- -CH 2 OCH 2 CH 2-
-CH2OCH2CH2CH2- -CH 2 OCH 2 CH 2 CH 2-
其中,作為特佳之Z1的構造,可列舉以下者。 Among them, as a particularly preferable structure of Z 1 , the following can be cited.
-CH2CH2CH2CH2- -CH 2 CH 2 CH 2 CH 2-
-CH2OCH2CH2CH2- -CH 2 OCH 2 CH 2 CH 2-
上述式(1)中,Q1係獨立至少包含(a+1)個矽原子之(a+1)價連接基,可成為環狀構造,可包含選自氧原子、氮原子及氟原子中之至少1種。作為如此之Q1的較佳者,分別可列舉具有(a+1)個Si原子之矽氧烷構造、非取代或鹵素取代之矽伸烷基構造、矽伸芳基構造或由此等之2種以上組合所構成之(a+1)價連接基。 In the above formula (1), Q 1 is an (a+1) valent linking group independently containing at least (a+1) silicon atoms, which can be a cyclic structure, and can contain oxygen atoms, nitrogen atoms and fluorine atoms At least one of them. As such a preferred Q 1 , siloxane structures having (a+1) Si atoms, unsubstituted or halogen-substituted silylene structures, silylene structures, or the like (A+1)-valent linking group composed of two or more combinations.
作為特佳之構造,具體而言,係表示下述之構造。 As a particularly preferable structure, specifically, the following structure is shown.
惟,a係與上述式(1)之a相同,分別獨立為1~10之整數,較佳為1~8之整數,更佳為1~4之整數。又,b為1~5之整數,較佳為3~5之整數。各單元之排列為無規,(a+1)個之各單元等之鍵結部係與1個Z1之末端(CH2等)及[ ]所包括之a個Z2的末端(CH2等)鍵結。 However, a is the same as a in the above formula (1), and is independently an integer from 1 to 10, preferably an integer from 1 to 8, and more preferably an integer from 1 to 4. In addition, b is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, (a+1) the bonding part of each unit, etc. is connected to the end of one Z 1 (CH 2 etc.) and the end of a Z 2 included in [] (CH 2 Etc.) Bonding.
於此,T為(a+1)價連接基,例如例示以下者。 Here, T is a (a+1)-valent linking group, for example, the following are illustrated.
其中,特佳之Q1係以下者。 Among them, the best Q 1 is below.
上述式(1)中,Z2係獨立為碳數1~200之亦可包含選自較佳為2~80之氧原子、氮原子及矽原子中之至少1種的2價烴基,途中可包含環狀構造。 In the above formula (1), Z 2 is independently a divalent hydrocarbon group having 1 to 200 carbon atoms and may also include at least one selected from the group consisting of oxygen atoms, nitrogen atoms, and silicon atoms, preferably 2 to 80. Contains ring structure.
作為Z2之較佳構造,可列舉以下者。 Z 2 as the preferred configuration, exemplified by the following.
-CH2- -CH 2-
-CH2CH2- -CH 2 CH 2-
-CH2CH2CH2- -CH 2 CH 2 CH 2-
-CH2CH2CH2CH2- -CH 2 CH 2 CH 2 CH 2-
-CH2CH2CH2CH2CH2CH2- -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2-
-CH2CH2CH2OCH2CH2- -CH 2 CH 2 CH 2 OCH 2 CH 2-
-CH2CH2CH2CH2OCH2CH2- -CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2-
-CH2CH2CH2[OC2H4]d[OC3H6]e[OC4H8]f- -CH 2 CH 2 CH 2 [OC 2 H 4 ] d [OC 3 H 6 ] e [OC 4 H 8 ] f-
於此,d為0~99之整數,e為0~66之整數,f為0~50之整數,合計若滿足碳數200以下即可。重複單位之配列不分種類為無規。又,各重複單位並非單體可為構 造異構體之混合物。 Here, d is an integer from 0 to 99, e is an integer from 0 to 66, and f is an integer from 0 to 50. The total number of carbons is less than 200. The arrangement of repeating units is random regardless of type. Moreover, each repeating unit is not a monomer but can be a structure Make a mixture of isomers.
作為Z2,作為特佳之構造,可列舉以下者,其中,適合d為1~30、e為1~30者。 As a particularly preferable structure of Z 2 , the following may be mentioned. Among them, those with d of 1-30 and e of 1-30 are suitable.
-CH2CH2CH2[OC2H4]d- -CH 2 CH 2 CH 2 [OC 2 H 4 ] d-
-CH2CH2CH2[OC3H6]e- -CH 2 CH 2 CH 2 [OC 3 H 6 ] e-
上述式(1)中,R1係獨立為氫原子、或含有:亦可包含選自氧原子及氮原子中之至少1種的丙烯醯基或α取代丙烯醯基之1價有機基,惟,R1係平均於1分子中至少具有1個含有前述丙烯醯基或α取代丙烯醯基之1價有機基。作為1價有機基,以於末端至少具有1個,較佳為具有1~5個丙烯醯基或α取代丙烯醯基之基較佳,作為該取代基,可列舉甲基、乙基、選自F、CF3、Cl及Br中之鹵素原子等。又,於構造途中可具有醯胺鍵、醚鍵、酯鍵等,尤其是作為R1O-基可包含胺基甲酸乙酯鍵(-NH(C=O)O-)者。作為如此R1之構造,例如可列舉以下者。 In the above formula (1), R 1 is independently a hydrogen atom, or a monovalent organic group containing at least one acryloyl group selected from an oxygen atom and a nitrogen atom or an α-substituted acryloyl group, but , R 1 is an average of at least one monovalent organic group containing the aforementioned acryloyl group or α-substituted acryloyl group in one molecule. As the monovalent organic group, it is preferred to have at least one at the end, preferably 1 to 5 acryloyl groups or α-substituted acryloyl groups. Examples of the substituent include methyl, ethyl, and From halogen atoms in F, CF 3 , Cl and Br, etc. In addition, it may have an amide bond, an ether bond, an ester bond, etc. in the middle of the structure, and in particular, the R 1 O- group may include a urethane bond (-NH(C=O)O-). Examples of the structure of such R 1 include the following.
CH2=CHCO- CH 2 =CHCO-
CH2=C(CH3)CO- CH 2 =C(CH 3 )CO-
CH2=C(C2H5)CO- CH 2 =C(C 2 H 5 )CO-
CH2=CFCO- CH 2 =CFCO-
CH2=CClCO- CH 2 =CClCO-
CH2=CBrCO- CH 2 =CBrCO-
CH2=C(CF3)CO- CH 2 =C(CF 3 )CO-
CH2=CHCOOCH2CH2-NHCO- CH 2 =CHCOOCH 2 CH 2 -NHCO-
CH2=C(CH3)COOCH2CH2-NHCO- CH 2 =C(CH 3 )COOCH 2 CH 2 -NHCO-
CH2=C(CH3)COOCH2CH2OCH2CH2-NHCO- CH 2 =C(CH 3 )COOCH 2 CH 2 OCH 2 CH 2 -NHCO-
(CH2=CHCOOCH2CH2)2C(CH3)-NHCO- (CH 2 =CHCOOCH 2 CH 2 ) 2 C(CH 3 )-NHCO-
其中,特別適合為以下者。 Among them, the following are particularly suitable.
CH2=CHCOOCH2CH2-NHCO- CH 2 =CHCOOCH 2 CH 2 -NHCO-
CH2=C(CH3)COOCH2CH2-NHCO- CH 2 =C(CH 3 )COOCH 2 CH 2 -NHCO-
在式(1)表示之含氟丙烯酸化合物,R1雖一部分可為氫原子,但並非全部為氫原子,係於1分子中平均包含1個以上之前述丙烯醯基及/或α取代丙烯醯基者。 In the fluorine-containing acrylic compound represented by formula (1), although part of R 1 may be hydrogen atoms, not all of them are hydrogen atoms, and it contains on average more than one acryloyl group and/or α-substituted acryloyl group in one molecule Base.
上述式(1)中,X為氟原子或-Z1-Q1-[Z2OR1]a表示之1價基。於此,Z1、Q1、Z2、R1、a係與上述相同。 In the above formula (1), X is a fluorine atom or a monovalent group represented by -Z 1 -Q 1 -[Z 2 OR 1 ] a . Here, Z 1 , Q 1 , Z 2 , R 1 , and a are the same as described above.
作為上述式(1)表示之含氟丙烯酸化合物,針對X為-Z1-Q1-[Z2OR1]a的情況,更具體而言,可表示以下之構造。 As the fluorine-containing acrylic compound represented by the above formula (1), when X is -Z 1 -Q 1 -[Z 2 OR 1 ] a , more specifically, the following structure can be represented.
(式中,Rf’為-CF2O(CF2O)p(CF2CF2O)qCF2-,p、q、p+q係與上述相同,例如q/p=0.9、p+q≒45。e1為1~30之整數,例如為2、4、9。R’為氫原子、
或
此等可混在於一個分子中。惟,R’係平均於1分子中至少含有1個上述(甲基)丙烯醯基之1價有機基)。 These can be mixed in one molecule. However, R'contains at least one monovalent organic group of the (meth)acryloyl group in one molecule on average).
作為上述式(1)表示之含氟丙烯酸化合物,針對X為氟原子時之較佳構造,具體而言可表示以下之構造。 As the fluorine-containing acrylic compound represented by the above formula (1), a preferable structure when X is a fluorine atom, specifically the following structure can be represented.
(式中,v1為2~120之整數,較佳為4~60之整數,e1、R’係如前述)。 (In the formula, v1 is an integer from 2 to 120, preferably an integer from 4 to 60, and e1 and R'are as described above).
此等之(A)成分可為單一或可為應用上述定義之複數化合物的混合物,混合物的情況下將相當於(A)之化合物之含量的合計作為(A)成分的含量計算即可。 These (A) components may be singular or may be a mixture of plural compounds as defined above. In the case of a mixture, the total content of the compounds corresponding to (A) may be calculated as the content of the (A) component.
在本發明之含氟丙烯酸組成物的第二必須成分,係於(B)1分子中包含1個或2個(甲基)丙烯醯基之丙烯酸化合物。(B)成分從與(A)成分之溶解性及與後述之(C)成分的混合性來看,在25℃之黏度為100mPa.s以下,較佳為0.4~20mPa.s。(B)成分之丙烯酸化合物係氫原子可部分性被氯原子(Cl)、氟原子(F)、或溴原子(Br)取代,可包含丙烯酸構造以外之氧原子、氮原子,亦可包含醚鍵、胺基甲酸乙酯鍵、異氰酸酯基、羥基。 The second essential component of the fluorine-containing acrylic composition of the present invention is (B) an acrylic compound containing one or two (meth)acryloyl groups in one molecule. The (B) component has a viscosity of 100 mPa at 25°C in terms of its solubility with (A) component and its compatibility with (C) component described later. s or less, preferably 0.4-20mPa. s. The hydrogen atom of the acrylic compound of component (B) may be partially substituted by chlorine atom (Cl), fluorine atom (F), or bromine atom (Br), and may contain oxygen and nitrogen atoms other than the acrylic structure, and may also contain ether Bond, urethane bond, isocyanate group, hydroxyl group.
作為如此之(B)成分當中,於分子中具有1個(甲基)丙烯醯基之化合物的較佳例,具體而言,表示下述 一般式(2)表示者。 As a preferable example of a compound having one (meth)acryloyl group in the molecule among such components (B), specifically, the following are shown General formula (2) said.
CH2=CR6COOR5 (2) CH 2 =CR 6 COOR 5 (2)
(式中,R5為碳數1~20,較佳為1~10之烷基、芳基或芳烷基,可為分支亦可為環狀,可包含脂肪族不飽和(雙)鍵、胺基甲酸乙酯鍵、醚鍵、異氰酸酯基、羥基。作為R5,具體而言,例如可列舉甲基、乙基、丙基、丁基、己基、環己基、苯基、二環戊烷基、二環戊烯基、糠基、四氫呋喃基、四氫吡喃基、-CH2CH2-OH、-CH2CH(CH3)-OH、-CH2CH2-NCO等。R6為氫原子或甲基、氟原子、碳數1~6之氟烷基,尤其是以氫原子、甲基、氟原子、三氟甲基較佳)。 (In the formula, R 5 is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, preferably 1 to 10, which may be branched or cyclic, and may contain aliphatic unsaturated (double) bonds, Ethyl urethane bond, ether bond, isocyanate group, hydroxyl group. Specific examples of R 5 include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl, and dicyclopentane group, a dicyclopentenyl group, furfuryl group, tetrahydrofuranyl, tetrahydropyranyl, -CH 2 CH 2 -OH, -CH 2 CH (CH 3) -OH, -CH 2 CH 2 -NCO like .R 6 It is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and a hydrogen atom, a methyl group, a fluorine atom, and a trifluoromethyl group are particularly preferred).
作為如此之化合物,更具體而言,可列舉甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、2-乙基-己基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯、異硬脂基(甲基)丙烯酸酯、2-(2-乙氧乙氧基)乙基(甲基)丙烯酸酯、四氫呋喃基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、苯氧基乙基丙烯酸酯、新戊二醇-丙烯酸-苯甲酸酯等。 As such compounds, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, isodecyl (meth)acrylate Ester, tridecyl (meth)acrylate, isostearyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofuran (meth)acrylate Acrylate, isobornyl (meth)acrylate, phenoxyethyl acrylate, neopentyl glycol-acrylic acid-benzoate, etc.
又,作為具有氧化乙烯、氧化丙烯、氧化四亞甲基、內酯等之重複單位構造,且具有各種烷氧基末端之丙烯酸酯化合物,例如即使是以甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙 二醇(甲基)丙烯酸酯、壬基酚EO加成物丙烯酸酯等之名稱市售之(甲基)丙烯酸化合物,若在25℃之黏度為100mPa.s以下亦可使用。 In addition, as an acrylate compound having a repeating unit structure of ethylene oxide, propylene oxide, tetramethylene oxide, lactone, etc., and various alkoxy groups, for example, methoxy polyethylene glycol (methyl )Acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polypropylene Glycol (meth)acrylate, nonylphenol EO adduct acrylate, etc. The commercially available (meth)acrylic compounds have a viscosity of 100mPa at 25°C. s or less can also be used.
又,作為於1分子中具有2個丙烯醯基之化合物,具體而言,可列舉1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯等。 In addition, as a compound having two acryloyl groups in one molecule, specific examples include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylic acid Ester, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, three Ethylene glycol di(meth)acrylate, nonanediol di(meth)acrylate, etc.
進而,作為(B)成分的一部分或全體,適合氫原子的一部分被F、Cl、Br取代者,尤其是期望為下述一般式(3)表示之丙烯酸化合物。 Furthermore, as a part or the whole of (B) component, it is suitable that a part of hydrogen atom is substituted by F, Cl, and Br, and it is especially desirable to be an acrylic compound represented by the following general formula (3).
CH2=CR2COOZ3Rf2 (3) CH 2 =CR 2 COOZ 3 Rf 2 (3)
上述式(3)中,R2係獨立為氫原子、F、Cl、Br或碳數1~8之1價烴基,烴基中之氫原子可被F、Cl、Br取代。 In the above formula (3), R 2 is independently a hydrogen atom, F, Cl, Br, or a monovalent hydrocarbon group with 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group may be substituted by F, Cl, or Br.
作為碳數1~8,尤其是碳數1~6之1價烴基,可列舉甲基、乙基等之烷基、三氟甲基等之氟烷基等。作為R2,較佳為氫原子、甲基。 Examples of monovalent hydrocarbon groups having 1 to 8 carbon atoms, especially carbon numbers 1 to 6, include alkyl groups such as methyl and ethyl groups, and fluoroalkyl groups such as trifluoromethyl groups. As R 2 , a hydrogen atom and a methyl group are preferable.
上述式(3)中,Z3係獨立為碳數1~8,尤其是碳數1~4之2價烴基,可成為分支,可於途中包含氧原子、羥基。 In the above formula (3), Z 3 is independently a carbon number of 1 to 8, especially a divalent hydrocarbon group of carbon number of 1 to 4, which may be branched and may contain an oxygen atom and a hydroxyl group in the middle.
作為特佳之Z3,可列舉以下者。 As particularly preferable Z 3 , the following can be cited.
-CH2- -CH 2-
-CH2CH2- -CH 2 CH 2-
-CH2-CH(OH)-CH2- -CH 2 -CH(OH)-CH 2-
-CH2-CH2-O-CH2CH2- -CH 2 -CH 2 -O-CH 2 CH 2-
上述式(3)中,Rf2為氟原子數2~20,尤其是1~10之氟烷基,可包含氫原子、氧原子,可成為分支。 In the above formula (3), Rf 2 is a fluoroalkyl group having 2 to 20 fluorine atoms, especially 1 to 10, which may contain hydrogen atoms and oxygen atoms, and may be branched.
作為Rf2,具體而言,係表示以下者。 As Rf 2 , specifically, it means the following.
-CF3 -CF 3
-C2F5 -C 2 F 5
-C3F7 -C 3 F 7
-C4F9 -C 4 F 9
-C6F13 -C 6 F 13
-CF2H -CF 2 H
-C2F4H -C 2 F 4 H
-CF2CF2H -CF 2 CF 2 H
-CF2CF2CF2CF2H -CF 2 CF 2 CF 2 CF 2 H
-CF2CF2CF2CF2CF2CF2H -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 H
-CF2CF2CF(CF3)2 -CF 2 CF 2 CF(CF 3 ) 2
-CF(CF3)2 -CF(CF 3 ) 2
-CH(CF3)2 -CH(CF 3 ) 2
-CF2CHFCF3 -CF 2 CHFCF 3
-CF2CF2OCF3 -CF 2 CF 2 OCF 3
作為滿足以上條件之(B)成分的丙烯酸化合物,可特別例示以下者。 As the acrylic compound of the component (B) satisfying the above conditions, the following can be specifically exemplified.
CH2=CHCOOCH2CH2C4F9 CH 2 =CHCOOCH 2 CH 2 C 4 F 9
CH2=CHCOOCH2CH2C6F13 CH 2 =CHCOOCH 2 CH 2 C 6 F 13
CH2=C(CH3)COOCH2CH2C4F9 CH 2 =C(CH 3 )COOCH 2 CH 2 C 4 F 9
CH2=C(CH3)COOCH2CH2C6F13 CH 2 =C(CH 3 )COOCH 2 CH 2 C 6 F 13
(B)成分可為單一或可為應用上述定義之複數化合物的混合物,混合物的情況下將相當於(B)之化合物之含量的合計作為(B)成分的含量計算即可。相當於(B)成分之化合物如有必要雖可以周知之方法合成,已市售來自試藥製造商等各種者,亦可直接使用此。 The component (B) may be a single component or a mixture of plural compounds as defined above. In the case of a mixture, the total content of the compound corresponding to (B) may be calculated as the content of the component (B). Although the compound corresponding to the component (B) can be synthesized by a known method if necessary, it is commercially available from various reagent manufacturers, etc., and can be used directly.
本發明之第一實施形態之含氟丙烯酸組成物,係將上述(A)、(B)成分作為必須成分,(A)成分與(B)成分的質量比為0.03<(A)/(B)<10,較佳為0.05≦(A)/(B)≦8,更佳為0.1≦(A)/(B)≦5的範圍內,尚且,未摻合不具有與丙烯醯基反應之基的揮發性有機化合物(尤其是於分子中未含有(甲基)丙烯醯基之非反應性揮發性有機化合物)者。 The fluorine-containing acrylic composition of the first embodiment of the present invention has the aforementioned (A) and (B) components as essential components, and the mass ratio of (A) component and (B) component is 0.03<(A)/(B) )<10, preferably 0.05≦(A)/(B)≦8, more preferably within the range of 0.1≦(A)/(B)≦5, and even if it is not blended, it does not have any reaction with acryl group Volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups) in the molecule.
作為本發明之其他實施形態,將該含氟丙烯酸組成物與後述之活性能量線硬化性組成物(E)混合,定為含氟活性能量線硬化性組成物,將此塗佈、硬化的情況下,雖可於基材上給予撥液性、防污性之硬化物層,但此撥液性、防污性係藉由分散於活性能量線硬化性組成物(E)的成分中之(A)成分存在於硬化物層表面來表現。因此,上述質量比(A)/(B)為0.03以下的情況下,含氟丙烯酸組成物中之(A)成分的含量過度縮小,最終之撥液性、防污性的表現變困難。另外,上述質量比(A)/(B)成為10以上的情況下, 因(A)成分之黏度的高度導致作業性降低,降低與(E)成分的相溶性或混合性。 As another embodiment of the present invention, the fluorine-containing acrylic composition and the active energy ray-curable composition (E) described later are mixed to form the fluorine-containing active energy ray-curable composition, and the case is applied and cured Next, although it is possible to provide a liquid-repellent and antifouling hardened layer on the substrate, the liquid-repellent and antifouling properties are achieved by being dispersed in the components of the active energy ray curable composition (E) ( A) The components are present on the surface of the hardened layer. Therefore, when the above-mentioned mass ratio (A)/(B) is 0.03 or less, the content of the (A) component in the fluorinated acrylic composition is excessively reduced, making it difficult to express the final liquid repellency and antifouling properties. In addition, when the mass ratio (A)/(B) is 10 or more, Due to the high viscosity of (A) component, the workability is reduced, and the compatibility or mixing with (E) component is reduced.
在本發明之第一實施形態之含氟丙烯酸組成物中,其製造方法並未特別限制,可混合在各種手法所製得之(A)成分及(B)成分。惟,(A)成分之丙烯酸化合物越提昇其撥液性、防污性的賦予特性,越提高黏度,有難以去除揮發分成為高黏度之化合物的傾向,於揮發分去除,有效之減壓、加熱等之條件引起(A)成分之構造中之丙烯醯基的聚合,增黏或凝膠化的危險大。因此,更佳為在丙烯醯基導入前之合成步驟,調製已去除揮發成分(不具有與丙烯醯基反應之基的揮發性有機化合物)的原料,使用此於(B)成分的存在下合成(A)成分,期望得到作為目的之含氟丙烯酸組成物。 In the fluorine-containing acrylic composition of the first embodiment of the present invention, the production method is not particularly limited, and the components (A) and (B) produced by various methods can be mixed. However, the acrylic compound of component (A) improves its liquid repellency and antifouling properties, and increases its viscosity. It tends to be difficult to remove volatiles and become high-viscosity compounds. When volatiles are removed, it is effective in reducing pressure, Conditions such as heating cause polymerization of the acryl group in the structure of component (A), and there is a high risk of thickening or gelation. Therefore, it is more preferable to prepare a raw material from which volatile components (volatile organic compounds that do not have a reactive group with the acryl group) have been removed in the synthesis step before the introduction of the acryl group, and use this to synthesize in the presence of component (B) (A) It is desired to obtain the target fluorine-containing acrylic composition for the component.
作為(A)成分之式(1)表示之含氟丙烯酸化合物之製造方法,例如首先,藉由使以往周知之方法所製造之具有下述一般式(5)表示之多官能Si-H基之氟聚醚化合物、X’-Rf1-Z1-Q1-[H]a (5) As the method for producing the fluorine-containing acrylic compound represented by the formula (1) of the component (A), for example, first, a polyfunctional Si-H group represented by the following general formula (5) is produced by a conventionally known method Fluoropolyether compound, X'-Rf 1 -Z 1 -Q 1 -[H] a (5)
(式中,Rf1、Z1、Q1、a係與上述相同,[ ]所包括之a個H係全部與Q1構造中之矽原子鍵結。X’為氟原子或-Z1-Q1-[H]a)、與下述一般式(6)表示之末端含有不飽和基之醇(於分子中具有烯基與醇性羥基之化合物)進行矽氫化反應,CH2=CR4-Z3-OH (6) (In the formula, Rf 1 , Z 1 , Q 1 , and a are the same as above, and the a H series included in [] are all bonded to the silicon atom in the Q 1 structure. X'is a fluorine atom or -Z 1- Q 1 -[H] a ), and the following general formula (6) with an unsaturated group-containing alcohol at the end (a compound having an alkenyl group and an alcoholic hydroxyl group in the molecule) for hydrosilation reaction, CH 2 =CR 4 -Z 3 -OH (6)
(式中,R4、Z3係矽氫化後所形成之-CH2-CHR4-Z3-構 造若為滿足在(1)式之Z2的要件者即可,R4與Z3可鍵結成為環狀構造) (In the formula, the -CH 2 -CHR 4 -Z 3 -structure formed by hydrogenation of R 4 and Z 3 is sufficient if it satisfies the requirements of Z 2 in formula (1), and R 4 and Z 3 can be Bonded into a ring structure)
而得到中間體之下述一般式(4)表示之含氟多官能醇化合物。 A fluorine-containing polyfunctional alcohol compound represented by the following general formula (4) as an intermediate is obtained.
X1-Rf1-Z1-Q1-[Z2OH]a (4) X 1 -Rf 1 -Z 1 -Q 1 -[Z 2 OH] a (4)
(式中,X1為氟原子或-Z1-Q1-[Z2OH]a表示之基,Rf1、Z1、Q1、Z2、a係如前述)。 (In the formula, X 1 is a fluorine atom or a group represented by -Z 1 -Q 1 -[Z 2 OH] a , and Rf 1 , Z 1 , Q 1 , Z 2 and a are as described above).
於此,作為具有上述式(5)表示之多官能Si-H基之氟聚醚化合物,可例示下述所示者。 Here, as the fluoropolyether compound having the polyfunctional Si-H group represented by the above formula (5), the following can be exemplified.
(式中,Rf’係與前述相同)。 (In the formula, Rf' is the same as above).
(式中,v1係與前述相同)。 (In the formula, v1 is the same as above).
又,作為上述式(6)表示之含有末端不飽和基之醇,可例示下述所示者。 In addition, as the terminal unsaturated group-containing alcohol represented by the above formula (6), the following can be exemplified.
CH2=CH-CH2-OH CH 2 =CH-CH 2 -OH
CH2=CH-CH2-OCH2CH2-OH CH 2 =CH-CH 2 -OCH 2 CH 2 -OH
CH2=CH-CH2-OCH2CH2CH2-OH CH 2 =CH-CH 2 -OCH 2 CH 2 CH 2 -OH
CH2=CH-CH2-OCH2CH(CH3)-OH CH 2 =CH-CH 2 -OCH 2 CH(CH 3 )-OH
CH2=CH-CH2-OCH2CH2CH2CH2-OH CH 2 =CH-CH 2 -OCH 2 CH 2 CH 2 CH 2 -OH
CH2=CH-CH2-(OCH2CH2)d1-OH CH 2 =CH-CH 2 -(OCH 2 CH 2 ) d1 -OH
CH2=CH-CH2-(OC3H6)e1-1-OCH2CH(CH3)-OH CH 2 =CH-CH 2 -(OC 3 H 6 ) e1-1 -OCH 2 CH(CH 3 )-OH
(式中,d1為1~30之整數,e1係與上述相同)。 (In the formula, d1 is an integer from 1 to 30, and e1 is the same as above).
此矽氫化(加成)反應係期望混合具有式(5)表示之多官能Si-H基之氟聚醚化合物、與式(6)表示之末端含有不飽和基之醇,鉑族金屬系之加成反應觸媒存在下,以反應溫度50~150℃,較佳為60~120℃進行1分鐘~48小時,尤其是10分鐘~12小時反應。反應溫度過低時,有反應未充分進行直接停止反應的情況,過高時,以因矽氫化之反應熱導致之溫度上昇變成無法調控反應,有引起暴沸或原料的分解等的情況。 This hydrosilation (addition) reaction is expected to mix a fluoropolyether compound having a polyfunctional Si-H group represented by formula (5), an alcohol with an unsaturated group at the end represented by formula (6), and a platinum group metal In the presence of the addition reaction catalyst, the reaction is carried out at a reaction temperature of 50-150°C, preferably 60-120°C, for 1 minute to 48 hours, especially 10 minutes to 12 hours. When the reaction temperature is too low, the reaction may not proceed sufficiently to stop the reaction. When it is too high, the reaction cannot be controlled due to the temperature rise caused by the reaction heat of hydrosilation, which may cause bumping or decomposition of raw materials.
此情況下,期望具有式(5)表示之多官能Si-H基之氟聚醚化合物、與式(6)表示之末端含有不飽和基之醇的反應比例,相對於具有式(5)表示之多官能Si-H基之氟聚醚化合物的[ ]所包括之H的總莫耳數,使用0.5~5.0倍莫耳式(6)表示之末端含有不飽和基之醇的末端不飽和基,尤其是使用0.9~2.0倍莫耳進行反應。式(6)表示之末端含有不飽和基之醇較此更少時,有得到具有高溶解性之含氟多官能醇化合物變困難的情況,較此以上更多時,降低反應溶液之均一性,反應速度變不安定,又,於反應後進行式(6)表示之末端含有不飽和基之醇的去除的情況下,僅剩餘之未反應的醇增加的部分有必要嚴格加熱、減壓、萃取等之條件。 In this case, it is expected that the reaction ratio of a fluoropolyether compound having a multifunctional Si-H group represented by the formula (5) and an alcohol having an unsaturated group at the end represented by the formula (6) is relative to that of the alcohol having a formula (5) The total number of moles of H included in the [] of the multifunctional Si-H-based fluoropolyether compound, using 0.5 to 5.0 times the moles of the terminal unsaturated group of the alcohol with an unsaturated group represented by the formula (6) , Especially using 0.9~2.0 times mole for reaction. When there are fewer alcohols with unsaturated groups at the end represented by formula (6) than this, it may become difficult to obtain a fluorine-containing polyfunctional alcohol compound with high solubility. When more than this, the uniformity of the reaction solution is reduced , The reaction rate becomes unstable, and when the unsaturation-containing alcohol at the end represented by the formula (6) is removed after the reaction, only the remaining unreacted alcohol must be heated, depressurized, Conditions for extraction, etc.
加成反應觸媒,例如可使用包含鉑、銠或鈀等之鉑族金屬之化合物。其中,較佳為包含鉑之化合物,可使用六氯鉑(IV)酸六水合物、鉑羰基乙烯基甲基錯合物、鉑-二乙烯基四甲基二矽氧烷錯合物、鉑-環乙烯基甲基矽氧烷錯合物、鉑-辛基醛/辛醇錯合物、或活性碳所載持之鉑。 As the addition reaction catalyst, for example, compounds containing platinum group metals such as platinum, rhodium or palladium can be used. Among them, compounds containing platinum are preferred, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complexes, platinum-divinyl tetramethyl disiloxane complexes, platinum -Cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, or platinum supported on activated carbon.
加成反應觸媒的摻合量,較佳為相對於具有式(5)表示之多官能Si-H基之氟聚醚化合物,加成反應觸媒所包含之金屬量成為0.1~5,000質量ppm的量,更佳為成為1~1,000質量ppm的量。 The blending amount of the addition reaction catalyst is preferably 0.1 to 5,000 mass ppm relative to the fluoropolyether compound having a multifunctional Si-H group represented by formula (5), and the amount of metal contained in the addition reaction catalyst More preferably, the amount is 1 to 1,000 ppm by mass.
上述之加成反應雖即使不存在溶劑亦可實施,但如有必要可用溶劑進行稀釋。此時稀釋溶劑雖可利用甲苯、二甲苯、異辛烷等一般被廣泛利用之有機溶劑,但較佳為沸點為作為目的之反應溫度以上且未阻礙反應,反應後所生成之含氟多官能醇化合物,可溶在上述反應溫度。作為如此之溶劑,例如期望六氟化間二甲苯、三氟甲苯(Benzotrifluoride)等之氟改質芳香族烴系溶劑、甲基全氟丁基醚等之氟改質醚系溶劑等之部分經氟改質的溶劑,尤其是以六氟化間二甲苯較佳。 The above-mentioned addition reaction can be carried out even in the absence of a solvent, but it can be diluted with a solvent if necessary. At this time, although toluene, xylene, isooctane and other commonly used organic solvents can be used as the dilution solvent, it is preferable that the boiling point is higher than the intended reaction temperature and does not hinder the reaction. The resulting fluorine-containing polyfunctional after the reaction The alcohol compound is soluble at the above reaction temperature. As such a solvent, for example, fluorine-modified aromatic hydrocarbon solvents such as meta-xylene hexafluoride and Benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are expected to be partially processed The fluorine-modified solvent is particularly preferably metaxylene hexafluoride.
使用溶劑的情況下,其使用量相對於具有式(5)表示之多官能Si-H基之氟聚醚化合物100質量份,較佳為5~2,000質量份,更佳為50~500質量份。若較此更少,藉由溶劑之稀釋效果變薄,若較多,稀釋度變過高,有導致反應速度降低的情況。 When a solvent is used, the amount used is relative to 100 parts by mass of the fluoropolyether compound having a multifunctional Si-H group represented by formula (5), preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass . If it is less than this, the dilution effect of the solvent becomes thinner, if it is more, the dilution becomes too high, which may result in a decrease in the reaction rate.
反應結束後,以減壓餾除未反應之式(6)表示之末端含有不飽和基之醇或稀釋溶劑,以萃取、吸附等之周知的方法去除較佳。此等之方法雖可單獨亦可組合複數之方法實施,尤其是在去除的最終階段,藉由使用減壓餾除或分子蒸餾,例如藉由內溫85℃以上且減壓0.133kPa以下等之條件,進行至停止餾分之餾出為止的餾除,期望將常壓且相當於沸點260℃以下之揮發性有機化合物的含量成為1質量%以下。 After the completion of the reaction, the unreacted alcohol or diluent solvent with unsaturated group at the end represented by formula (6) is removed by vacuum distillation, and it is preferably removed by well-known methods such as extraction and adsorption. Although these methods can be implemented individually or in combination with multiple methods, especially in the final stage of removal, by using vacuum distillation or molecular distillation, for example, by using an internal temperature of 85°C or higher and a reduced pressure of 0.133kPa or less. The condition is to perform distillation until the distillation of the fraction is stopped, and it is desirable that the content of the volatile organic compound corresponding to a boiling point of 260° C. or less under normal pressure is 1% by mass or less.
作為如此進行所得之式(4)表示之含氟多官能醇化合物,可例示下述所示者。 As the fluorine-containing polyfunctional alcohol compound represented by formula (4) obtained in this way, the following can be exemplified.
(式中,Rf’、e1、v1係與上述相同)。 (In the formula, Rf', e1, and v1 are the same as above).
其次,藉由於上述所得之含氟多官能醇化合物導入丙烯醯基,可得到含氟丙烯酸化合物(A)。 Secondly, the fluorine-containing acrylic compound (A) can be obtained by introducing an acrylic group into the fluorine-containing polyfunctional alcohol compound obtained above.
本發明之其他實施形態,係將如以上般進行所得之上述式(4)表示之含氟多官能醇化合物作為(C)成分,於前述之(B)成分存在下,使於1分子中具有一個異氰酸酯基與至少一個(甲基)丙烯醯基之化合物(D)進行反應來合成(A)成分,而得到本發明之第一實施形態即含氟丙烯酸組成物之方法。 In another embodiment of the present invention, the fluorine-containing polyfunctional alcohol compound represented by the above formula (4) obtained as described above is used as the component (C), and in the presence of the component (B) described above, it has The compound (D) of one isocyanate group and at least one (meth)acryloyl group is reacted to synthesize component (A) to obtain the first embodiment of the present invention, which is a method of fluorine-containing acrylic composition.
作為於1分子中具有一個異氰酸酯基與至少一個(甲基)丙烯醯基之化合物(D),可列舉下述所示者。 As the compound (D) having one isocyanate group and at least one (meth)acryloyl group in one molecule, the following can be cited.
CH2=CHCOOCH2CH2-N=C=O CH 2 =CHCOOCH 2 CH 2 -N=C=O
CH2=CCH3COOCH2CH2-N=C=O CH 2 =CCH 3 COOCH 2 CH 2 -N=C=O
CH2=CCH3COOCH2CH2OCH2CH2-N=C=O CH 2 =CCH 3 COOCH 2 CH 2 OCH 2 CH 2 -N=C=O
[CH2=CCH3COOCH2]2CH(CH3)-N=C=O [CH 2 =CCH 3 COOCH 2 ] 2 CH(CH 3 )-N=C=O
其中,特佳為以下之2種。 Among them, particularly preferred are the following two types.
CH2=CHCOOCH2CH2-N=C=O CH 2 =CHCOOCH 2 CH 2 -N=C=O
CH2=CCH3COOCH2CH2-N=C=O CH 2 =CCH 3 COOCH 2 CH 2 -N=C=O
(D)成分雖可相對於(C)成分之羥基量的合計,作為異氰酸酯基置入等莫耳以上使其進行反應,使羥基全部反應進行胺基甲酸乙酯化,但相對於(C)成分1莫耳進行平均,若導入1莫耳以上之丙烯醯基即可,藉由使羥基與異氰酸酯基等量或使羥基稍微過剩,可減少未反應(D)成分的殘存量。具體而言,期望將相當於反應系中之(C)成 分之全化合物量定為x莫耳,將(C)成分之羥基量的合計定為y莫耳的情況下,(D)成分的摻合量為x莫耳以上1.05y莫耳以下,特佳為0.5y莫耳以上1.0y莫耳以下。(D)成分過少的情況下,提高殘存完全未導入丙烯醯基之(C)成分的可能性,有導致降低最終之組成物的硬化性或生成物的溶解性的可能性。(D)成分過多的情況下,(D)成分的殘存量增大,有導致對最終之組成物的防污性能給予影響的可能性。 Although the component (D) can be reacted by placing equal mol or more with respect to the total amount of the hydroxyl groups of the component (C) as an isocyanate group, and reacting all the hydroxyl groups to urethane, it is relative to (C) The component 1 mol is averaged, and if 1 mol or more of acryloyl group is introduced, the remaining amount of unreacted (D) component can be reduced by making the hydroxyl group equal to the isocyanate group or making the hydroxyl group slightly excessive. Specifically, it is expected to be equivalent to (C) in the reaction system In the case where the total amount of the compound is divided into x mol, and the total amount of hydroxyl groups of the component (C) is defined as y mol, the blending amount of the component (D) is x mol or more and 1.05 mol or less. Preferably, it is 0.5 y mol or more and 1.0 y mol or less. When the component (D) is too small, the possibility that the component (C) into which the acryl group has not been introduced will remain at all is increased, and the curability of the final composition or the solubility of the product may be reduced. When there are too many components (D), the remaining amount of the component (D) increases, which may affect the antifouling performance of the final composition.
反應時之(B)、(C)、(D)各成分的混合比率,(D)成分的摻合量為1.0y以下,且於反應後未殘存(D)成分的情況下,以質量比滿足以下較佳。 The mixing ratio of each component (B), (C), (D) during the reaction, the blending amount of (D) component is 1.0y or less, and if (D) component does not remain after the reaction, the mass ratio It is better to satisfy the following.
0.03<[(C)+(D)]/(B)<5 0.03<[(C)+(D)]/(B)<5
又,(D)成分的摻合量較1.0y更大,反應後殘存(D)成分的情況,殘存之(D)成分認定可作為(B)成分之一部分。亦即,將殘存(D)成分以外所包含之(B)成分定為(B1),將相當於1.0y之(D)成分的質量定為(d1),從經摻合之全(D)成分的質量減去(d1)之值定為(d2)的情況下,以滿足以下較佳。 In addition, if the blending amount of component (D) is greater than 1.0y, and component (D) remains after the reaction, the remaining component (D) is recognized as part of component (B). That is, the (B) component contained other than the remaining (D) component is designated as (B1), and the mass of the (D) component equivalent to 1.0 y is designated as (d1), from the blended total (D) When the value of the component mass minus (d1) is set as (d2), it is better to satisfy the following requirements.
0.03<[(C)+(d1)]/[(B1)+(d2)]<5 0.03<[(C)+(d1)]/[(B1)+(d2)]<5
又,反應時如有必要可添加阻聚劑。作為阻聚劑雖並未特別限制,但通常可使用作為丙烯酸化合物之阻聚劑使用者。具體而言,可列舉氫醌、氫醌單甲基醚、4-tert-丁基兒茶酚、二丁基羥基甲苯等。 In addition, a polymerization inhibitor can be added if necessary during the reaction. Although it is not particularly limited as a polymerization inhibitor, it can usually be used as a polymerization inhibitor for acrylic compounds. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be mentioned.
此等之摻合量期望(B)、(C)、(D)成分的合計質量之1 ~3,000ppm,更佳為1~500ppm。 The blending amount is expected to be 1 of the total mass of components (B), (C), and (D) ~3,000ppm, more preferably 1~500ppm.
在此反應,為了增加反應的速度可加入適當之觸媒。作為觸媒,例如例示有二丁基二乙酸錫、二丁基二月桂酸錫、二丁基二辛酸(Dioctate)錫、二辛基二乙酸錫、二辛基二月桂酸錫、二辛基二辛酸(Dioctoate)錫、二辛酸亞錫等之烷基錫酯化合物、四異丙氧基鈦、四n-丁氧基鈦、肆(2-乙基己氧基)鈦、二丙氧基雙(乙醯丙酮基)鈦、鈦異丙氧基辛二醇等之鈦酸酯或鈦螯合劑化合物、鋯四乙醯丙酮、鋯三丁氧基單乙醯丙酮、鋯單丁氧基乙醯丙酮雙(乙基乙醯乙酸酯)、鋯二丁氧基雙(乙基乙醯乙酸酯)、鋯四乙醯丙酮、鋯螯合劑化合物等。此等並非限定於其1種,雖可作為2種或2種以上之混合物使用,但尤其是以對環境之影響低的鈦化合物、鋯化合物的使用較佳。 In this reaction, an appropriate catalyst can be added in order to increase the reaction speed. As the catalyst, for example, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctanoate (Dioctate) tin, dioctyl tin diacetate, dioctyl tin dilaurate, and dioctyl tin are exemplified. Dioctanoate (Dioctoate) tin, stannous dioctoate and other alkyl tin ester compounds, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis (2-ethylhexyloxy), dipropoxy Bis(acetylacetonyl) titanium, titanium isopropoxy octanediol, etc. titanate or titanium chelating agent compound, zirconium tetraacetone, zirconium tributoxymonoacetone, zirconium monobutoxyacetone Zirconium acetone bis (ethyl acetyl acetate), zirconium dibutoxy bis (ethyl acetyl acetate), zirconium tetraacetone acetone, zirconium chelating agent compounds, etc. These are not limited to one type, and although they can be used as a mixture of two or more types, it is particularly preferable to use titanium compounds and zirconium compounds that have a low environmental impact.
相對於反應物總質量((C)、(D)成分的合計質量),藉由將此等之觸媒加入0.01~2質量%,較佳為0.05~1質量%,可使反應速度增加。 With respect to the total mass of the reactants (the total mass of the components (C) and (D)), the reaction rate can be increased by adding these catalysts to 0.01-2% by mass, preferably 0.05-1% by mass.
反應如有必要將(B)、(C)、(D)各成分與上述之阻聚劑或觸媒一起進行攪拌混合,如有必要進行加熱,使反應進行。 Reaction If necessary, each component of (B), (C), (D) and the above-mentioned polymerization inhibitor or catalyst are stirred and mixed, and if necessary, heating is carried out to make the reaction proceed.
反應係以0~120℃,較佳為10~70℃的溫度,1分鐘~500小時,較佳為10分鐘~48小時進行。反應溫度過低時,有反應速度變過度遲緩的情況,反應溫度過高時,有作為副反應引起丙烯醯基之聚合的可能性。 The 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. When the reaction temperature is too low, the reaction rate may become excessively slow, and when the reaction temperature is too high, there is a possibility of polymerization of the acryl group as a side reaction.
反應結束後,如有必要可藉由吸附處理或過 濾洗淨等之方法,去除著色成分或不溶成分,而得到本發明之含氟丙烯酸組成物。 After the reaction, if necessary, it can be treated by adsorption or over The coloring component or insoluble component is removed by methods such as filtration and washing to obtain the fluorine-containing acrylic composition of the present invention.
如此進行所得之含氟丙烯酸組成物,成為未摻合揮發性有機化合物者。 The fluorine-containing acrylic composition obtained in this way becomes one that is not blended with volatile organic compounds.
本發明之含氟丙烯酸組成物,添加在後述之活性能量線硬化性組成物(E),可成為含氟活性能量線硬化性組成物。 The fluorine-containing acrylic composition of the present invention can be added to the active energy ray curable composition (E) described later to become a fluorine-containing active energy ray curable composition.
本發明之一個實施形態所使用之活性能量線硬化性組成物(E),若為藉由紫外線、電子束等之活性能量線的照射給予硬化物者,雖並未特別限制,但尤其是以包含丙烯酸化合物(Ea)、光聚合起始劑(Eb)較佳。 The active energy ray curable composition (E) used in one embodiment of the present invention is not particularly limited if it is administered to the cured product by irradiation of active energy rays such as ultraviolet rays, electron beams, etc., but especially It is preferable to contain an acrylic compound (Ea) and a photopolymerization initiator (Eb).
作為丙烯酸化合物(Ea),無論1官能、多官能皆可使用。例如,雖亦可使用上述之(B)成分即1官能及2官能之丙烯酸化合物,但作為(Ea)成分,尤其是以包含於1分子中具有2個以上丙烯醯基之非氟化丙烯酸化合物較佳。 As the acrylic compound (Ea), both monofunctional and polyfunctional can be used. For example, although the above-mentioned component (B), namely, monofunctional and bifunctional acrylic compounds can also be used, as the component (Ea), it is especially a non-fluorinated acrylic compound containing two or more acryl groups in one molecule Better.
作為如此之非氟化丙烯酸化合物,若為於1分子中具有2個以上丙烯醯基或α取代丙烯醯基者即可,例如可列舉包含將1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、異氰脲酸氧化乙烯改質二(甲基)丙烯酸酯、異氰脲酸EO改質三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、參(甲基)丙烯醯氧基乙基磷酸酯、苯二甲酸氫-(2,2,2-三-(甲基)丙烯醯 氧基甲基)乙酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯等之2~6官能之(甲基)丙烯酸化合物、此等之(甲基)丙烯酸化合物於氧化乙烯、氧化丙烯、環氧氯丙烷、脂肪酸、烷基改質品、環氧樹脂加成丙烯酸,並於所得之環氧基丙烯酸酯類、及丙烯酸酯共聚物的側鏈導入(甲基)丙烯醯基之共聚物等。 As such a non-fluorinated acrylic compound, if it has two or more acryl groups or α-substituted acryl groups in one molecule, for example, the compound includes 1,6-hexanediol di(meth)acrylic acid Ester, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanurate ethylene oxide modified di(meth)acrylate, isocyanurate EO modified three ( Meth) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, ginseng (meth)acryloxyethyl phosphate , Hydrogen phthalate-(2,2,2-tris-(meth)acrylic acid) Oxymethyl) ethyl ester, 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 other 2~6 functional (meth)acrylic compounds, these (meth)acrylic compounds are used in ethylene oxide, propylene oxide, Epichlorohydrin, fatty acids, alkyl modified products, epoxy resins are added with acrylic acid, and (meth)acrylic acid copolymers are introduced into the side chains of the obtained epoxy acrylates and acrylate copolymers Wait.
又,亦可使用胺基甲酸乙酯丙烯酸酯類、使於聚異氰酸酯具有羥基之(甲基)丙烯酸酯進行反應所得者、使於聚異氰酸酯與末端二醇之聚酯具有羥基之(甲基)丙烯酸酯進行反應所得者、於多元醇使過剩之二異氰酸酯進行反應所得之聚異氰酸酯使具有羥基之(甲基)丙烯酸酯進行反應所得者。其中,較佳為選自2-羥基乙基(甲基)丙烯酸酯、2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、及季戊四醇三丙烯酸酯中之具有羥基之(甲基)丙烯酸酯、與使選自六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、甲伸苯基二異氰酸酯、賴胺酸二異氰酸酯、降莰烷二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、亞甲基雙(4-環己基異氰酸酯)、2-甲基-1,3-二異氰酸基環己烷、2-甲基-1,5-二異氰酸基環己烷及二苯基甲烷二異氰酸酯中之聚異氰酸酯進行反應之胺基甲酸乙酯丙烯酸酯類。 In addition, urethane acrylates, those obtained by reacting (meth)acrylates having hydroxyl groups in polyisocyanates, and (meth) having hydroxyl groups in polyesters of polyisocyanates and terminal diols can also be used. Those obtained by reacting acrylates, or those obtained by reacting excess diisocyanates with polyols, and those obtained by reacting (meth)acrylates having hydroxyl groups in polyisocyanates. Among them, it is preferably a (methyl) group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate. Acrylate, and use selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylmethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanate Methyl)cyclohexane, methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanate Urethane acrylates in which the polyisocyanate in cyclohexane and diphenylmethane diisocyanate reacts.
尤其是可列舉於1分子中具有2個以上丙烯醯基或α取代丙烯醯基且不具有胺基甲酸乙酯鍵之多官能丙 烯酸化合物、或包含由此多官能丙烯酸化合物、與使脂肪族聚異氰酸酯與具有羥基之丙烯酸化合物進行反應所得之於1分子中具有3個以上丙烯醯基或α取代丙烯醯基之多官能胺基甲酸乙酯丙烯酸酯類所構成者中之至少2種類之丙烯酸化合物的混合物。 In particular, polyfunctional acrylics having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and no urethane bond can be cited. Acrylic acid compound, or a polyfunctional amine containing three or more acryloyl groups or α-substituted acryloyl groups in one molecule, obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group, containing the multifunctional acrylic compound A mixture of at least two types of acrylic compounds among the ethyl formate acrylates.
於此,作為於1分子中具有2個以上丙烯醯基或α取代丙烯醯基,且不具有胺基甲酸乙酯鍵之多官能丙烯酸化合物,可列舉三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯、及將此等以氧化乙烯或氧化丙烯改質之化合物。 Here, as a multifunctional acrylic compound having two or more acryloyl groups or α-substituted acryloyl groups in one molecule, and no urethane bond, trimethylolpropane tri(meth)acrylic acid can be cited Ester, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and these compounds modified with ethylene oxide or propylene oxide.
作為使脂肪族聚異氰酸酯與具有羥基之丙烯酸化合物進行反應所得之於1分子中具有3個以上丙烯醯基或α取代丙烯醯基之多官能胺基甲酸乙酯丙烯酸酯類,可表示於六亞甲基二異氰酸酯、降莰烷二異氰酸酯、異佛爾酮二異氰酸酯及此等之3量化物、及此等之2官能、3官能之異氰酸酯類使脂肪族二醇、脂肪族多元醇及於側鏈具有羥基之聚丙烯酸酯類進行反應所得之2官能以上的聚異氰酸酯,使三羥甲基丙烷二(甲基)丙烯酸酯、甘油(Glycerin)二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯氧基乙基)羥基乙基異氰脲酸酯、季戊四醇三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯及此 等之氧化乙烯、氧化丙烯改質體進行反應者、或使脂肪族多元醇及於側鏈具有羥基之聚丙烯酸酯類與2-異氰酸基乙基(甲基)丙烯酸酯或1,1-(雙丙烯醯氧基甲基)乙基異氰酸酯等之具有異氰酸酯基之丙烯酸化合物進行反應者。 As a polyfunctional ethyl urethane acrylate having three or more acryl groups or α-substituted acryl groups in one molecule obtained by reacting aliphatic polyisocyanates with an acrylic compound having a hydroxyl group, it can be expressed in hexadecane Methyl diisocyanate, norbornane diisocyanate, isophorone diisocyanate and these 3 quantified products, and these difunctional and trifunctional isocyanates make aliphatic diols, aliphatic polyols and side The polyisocyanate obtained by reacting polyacrylates with hydroxyl groups in the chain is a polyisocyanate with two or more functionalities, which is trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-( (Meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester and this Reactors such as ethylene oxide and propylene oxide reformers, or make aliphatic polyols and polyacrylates with hydroxyl groups on the side chains and 2-isocyanatoethyl (meth)acrylate or 1,1 -(Bisacryloxymethyl) ethyl isocyanate and other acrylic compounds having isocyanate groups to react.
進而,作為(Ea)成分,不僅液狀之成分,亦可包含以丙烯醯基修飾微粒子狀之高分子量體的表面或無機填料微粒子的表面者。 Furthermore, as the component (Ea), not only a liquid component, but also the surface of a fine particle-shaped high molecular weight body or the surface of an inorganic filler fine particle is modified with an acryl group.
如以上之(Ea)成分,雖即使1種單獨亦可使用,但亦可摻合相當於用以提高塗佈性或硬化後被膜的特性之複數化合物來使用。 The above-mentioned (Ea) component can be used singly, but it can also be used by blending a plurality of compounds corresponding to the properties of the coating film after coating or curing.
又,作為(Eb)成分,藉由含有光聚合起始劑,可成為提高使用紫外線作為活性能量線時之硬化性的硬化性組成物。 Furthermore, by containing a photopolymerization initiator as the component (Eb), it can be a curable composition that improves the curability when using ultraviolet rays as the active energy rays.
(Eb)成分之光聚合起始劑,若為可藉由紫外線照射使丙烯酸化合物硬化者,雖並未特別限定,但較佳為例如可列舉苯乙酮、二苯甲酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁酮-1、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎咻基)苯基]-1-丁酮、2,4,6-三甲基苯甲醯基-二苯基-膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、1,2-辛烷二酮-1-[4-(苯硫基)-2-(o-苯甲醯基肟)]、乙酮-1-[9-乙基-6-(2-甲基苯甲醯 基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、2-羥基-1-{4-[4-(2-羥基-2-甲基丙醯基)苄基]苯基}-2-甲基丙烷-1-酮等,可1種單獨亦可併用2種以上。 The photopolymerization initiator of the component (Eb) is not particularly limited if it is capable of curing the acrylic compound by ultraviolet irradiation, but preferably, acetophenone, benzophenone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[ 4-(2-Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Morpholinyl propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) butanone-1, 2-(dimethylamino)-2- [(4-Methylphenyl)methyl]-1-[4-(4-morphoyl)phenyl]-1-butanone, 2,4,6-trimethylbenzyl-diphenyl Benzyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2 -(o-benzyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzyl oxime) Yl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl Yl]phenyl}-2-methylpropan-1-one, etc., may be used alone or in combination of two or more kinds.
(Eb)成分的含量雖可因應硬化條件與藉由作為目的之活性能量線硬化性組成物(E)之硬化物的物性適當決定,但期望例如相對於(Ea)成分的合計100質量份成為0.1~15質量份,尤其是成為1~10質量份的量。添加量較此更少時,有降低硬化性的情況,較此更多時,恐有增大對硬化後之物性的影響之虞。 Although the content of the component (Eb) can be appropriately determined according to the curing conditions and the physical properties of the cured product of the curable composition (E) by the intended active energy ray, it is desirable, for example, to be relative to the total 100 parts by mass of the component (Ea) 0.1 to 15 parts by mass, especially 1 to 10 parts by mass. When the amount of addition is smaller than this, the hardenability may decrease, and when it is larger than this, the effect on the physical properties after hardening may increase.
活性能量線硬化性組成物(E)中,除此之外亦可摻合硫醇化合物或馬來醯亞胺化合物等、丙烯醯基以外之活性能量線反應性化合物、有機溶劑、阻聚劑、防靜電劑、消泡劑、黏度調整劑、耐光安定劑、耐熱安定劑、抗氧化劑、界面活性劑、著色劑、及高分子或無機物之填料等。此等並未特別限制其構造,於不損及本發明之目的的範圍,可使用周知者。 In addition to the active energy ray curable composition (E), thiol compounds, maleimide compounds, etc., active energy ray reactive compounds other than acryl, organic solvents, and polymerization inhibitors can also be blended , Antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers. These do not particularly limit the structure, and well-known ones can be used within the scope not to impair the purpose of the present invention.
又,作為活性能量線硬化性組成物(E),作為已摻合(Ea)、(Eb)成分及各種添加物之活性能量線硬化性組成物,可將從各公司以塗料、油墨、硬塗劑等之分類市售之既存的組成物作為(E)成分的一部分或全體使用。如此即使使用市售品之硬塗劑的情況,因應目的,可追加有機溶劑、阻聚劑、防靜電劑、消泡劑、黏度調整劑、耐光安定劑、耐熱安定劑、抗氧化劑、界面活性劑、著色劑、及填料等進行摻合。 In addition, as active energy ray curable composition (E), as active energy ray curable composition blended with components (Ea) and (Eb) and various additives, coatings, inks, and hardeners can be used from various companies Classification of paints, etc. Existing commercially available compositions are used as part or all of component (E). Even when using commercially available hard coat agents, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, and interfacial activity can be added to suit the purpose. Agents, colorants, and fillers are blended.
本發明之一個實施形態,係一種含氟活性能量線硬化性組成物,其特徵為相對於上述之活性能量線硬化性組成物(E)100質量份,包含本發明之第一實施形態即含氟丙烯酸組成物0.005~40質量份,較佳為0.01~20質量份。含氟丙烯酸組成物的摻合量若為上述範圍雖未特別限制,但期望進一步作為含氟丙烯酸組成物中之(A)成分之摻合量為含氟活性能量線硬化性組成物中之0.005~10質量%。(A)成分量較此以上更少時,形成硬化物時,無法將(A)成分充分配置在表面,無法顯示期待之撥液性、防污性,較此更大時,對於硬化物層的強度或硬度之(A)成分的影響變過大,將失去原本之活性能量線硬化性組成物(E)的硬化物特性。 An embodiment of the present invention is a fluorine-containing active energy ray curable composition characterized by containing 100 parts by mass of the above-mentioned active energy ray curable composition (E), which is the first embodiment of the present invention. The fluoroacrylic acid composition is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass. The blending amount of the fluorinated acrylic composition is not particularly limited if it is in the above range, but it is desirable that the blending amount of the (A) component in the fluorinated acrylic composition is 0.005 in the fluorinated active energy ray curable composition. ~10% by mass. When the amount of component (A) is less than this, when the hardened product is formed, component (A) cannot be fully arranged on the surface, and the expected liquid repellency and antifouling properties cannot be displayed. When it is larger than this, the hardened layer If the influence of the component (A) on the strength or hardness of the active energy ray becomes too large, the original hardened properties of the active energy ray curable composition (E) will be lost.
若為如以上進行所得之本發明之含氟活性能量線硬化性組成物,可抑制不組入硬化物的構造之揮發性有機化合物的含有,成為於任意基材的表面可形成防污性、撥液性優異之硬化樹脂層之揮發性有機化合物的發生極為少之硬化性組成物。 If the fluorine-containing active energy ray curable composition of the present invention obtained as described above can suppress the content of volatile organic compounds that are not incorporated into the structure of the cured product, it can form antifouling properties on the surface of any substrate. A curable composition with extremely low generation of volatile organic compounds in the cured resin layer with excellent liquid repellency.
進而於本發明,提供一種將上述之本發明之含氟活性能量線硬化性組成物塗佈在基材表面使其硬化之物品。如上述,若使用本發明之含氟活性能量線硬化性組成物,可於基材的表面形成具有優異之表面特性的硬化被膜(硬化樹脂層)。尤其是由於於丙烯酸硬塗的表面賦予撥水性、撥油性、防污性故為有用。藉此,可將因指紋、皮脂、汗等之人脂、化妝品等導致之污染難以附著,且擦拭 性亦優異之硬塗表面附予在基材(物品)。因此,本發明之含氟活性能量線硬化性組成物,可提供一種對於有人體接觸因人脂、化妝品等導致污染的可能性之基材(物品)的表面之塗裝膜或保護膜。 Furthermore, in the present invention, there is provided an article in which the above-mentioned fluorine-containing active energy ray curable composition of the present invention is applied to the surface of a substrate to be cured. As described above, if the fluorine-containing active energy ray curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of the substrate. In particular, it is useful because it imparts water repellency, oil repellency, and antifouling properties to the acrylic hard-coated surface. With this, it is difficult to adhere to the pollution caused by fingerprints, sebum, sweat and other human grease, cosmetics, etc., and wipe off The hard-coated surface with excellent performance is attached to the substrate (article). Therefore, the curable fluorine-containing active energy ray composition of the present invention can provide a coating film or a protective film for the surface of a substrate (article) that may be contaminated by human body contact with human fat, cosmetics, etc.
使用本發明之含氟活性能量線硬化性組成物而形成之硬化被膜(硬化樹脂層),可藉由直接塗佈於賦予特性之物品的表面使其硬化、或將於各種基材上塗佈本發明之含氟活性能量線硬化性組成物製作硬化膜之薄膜貼附在目的之物品的表面,對各式各樣的物品賦予特性。 The cured film (cured resin layer) formed by using the fluorine-containing active energy ray curable composition of the present invention can be cured by directly coating on the surface of a property-provided article, or coated on various substrates The cured film of the fluorine-containing active energy ray curable composition of the present invention is attached to the surface of the target article to impart characteristics to various articles.
於此,作為本發明之含氟活性能量線硬化性組成物的塗佈方法,雖並未特別限制,但例如可使用輥塗、凹版塗佈、流塗、浸塗、噴塗、旋塗、棒塗、絲網印刷等之周知的塗佈方法。塗佈後於塗膜照射活性能量線將此硬化。於此,作為活性能量線,雖可使用電子束、紫外線等任意者,但尤其是以紫外線較佳。作為紫外線源,適合水銀燈、金屬鹵化物燈、LED燈。作為紫外線照射量,由於有過少時,殘存未硬化成分,過多時,塗膜及基材劣化的可能性,故期望為10~10,000mJ/cm2,尤其是20~4,000mJ/cm2的範圍。又,為了防止因氧導致之硬化阻礙,可於紫外線照射時將照射環境以氮、二氧化碳、氬等之未包含氧分子之惰性氣體取代、或可將塗膜表面以具有脫模性之有紫外線透過性之保護層被覆,從其上照射紫外線、或基材具有紫外線透過性的情況下,可將塗膜表面以脫模性之保護層被覆之外,並從與基材的塗佈面相反側照 射紫外線。又,為了有效果地進行塗膜之整平或塗膜中之丙烯醯基的聚合,可於紫外線照射前及照射中將塗膜及基材以熱風乾燥爐等任意手法加熱。 Here, the coating method of the curable fluorine-containing active energy ray composition of the present invention is not particularly limited, but for example, roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating can be used. Well-known coating methods such as coating and screen printing. After coating, the coating film is irradiated with active energy rays to harden it. Here, as the active energy ray, any of electron beams and ultraviolet rays can be used, but ultraviolet rays are particularly preferred. As the ultraviolet source, mercury lamps, metal halide lamps, and LED lamps are suitable. As the ultraviolet irradiation amount, because too small, the remaining uncured component, is too large, the possibility of deterioration of the coating and the substrate, it is desirably 10 ~ 10,000mJ / cm 2, especially in the range of 20 ~ 4,000mJ / cm 2 of . In addition, in order to prevent the hardening caused by oxygen, the irradiation environment can be replaced with inert gases that do not contain oxygen molecules such as nitrogen, carbon dioxide, argon, etc., or the surface of the coating film can be releasable with ultraviolet rays. A transparent protective layer is coated. When ultraviolet rays are irradiated from it, or the substrate has ultraviolet transmittance, the surface of the coating film can be covered with a mold-releasing protective layer, and from the opposite to the coated surface of the substrate The side is irradiated with ultraviolet rays. In addition, in order to effectively level the coating film or polymerize the acryl group in the coating film, the coating film and the substrate can be heated by any method such as a hot air drying oven before and during ultraviolet irradiation.
又,使用本發明之含氟活性能量線硬化性組成物所形成之硬化被膜(硬化樹脂層)的厚度,雖並非被特別限定者,但所得之膜厚過薄的情況下,得不到充分之表面硬度,又過厚時,降低硬塗膜的機械性強度,從容易陷入裂縫的點來看,通常為5nm~100μm,尤其是以1μm~20μm較佳。 In addition, although the thickness of the cured film (cured resin layer) formed using the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, if the resulting film thickness is too thin, sufficient If the surface hardness is too thick, the mechanical strength of the hard coating film will be reduced. From the point of view that it is easy to fall into cracks, it is usually 5nm~100μm, especially 1μm~20μm.
作為如此之物品,例如作為平板型電腦、手機.智慧型手機等之移動(通信)的信息終端、筆記型電腦、數位媒體播放裝置、錶型.眼鏡型穿戴式電腦、數位相機、數位攝影機、電子圖書閱讀器等以人手持有走路之各種機器的框體;液晶顯示器、電漿顯示器、有機EL顯示器、背投型顯示器、螢光顯示管(VFD)、場致發射投影顯示器、CRT、色粉顯示器(toner display)等之各種平板顯示器及TV之畫面等之表示操作機器表面、汽車之外裝、鋼琴或家具之光澤表面、大理石等之建築用石材表面、廁所、浴室、盥洗室等之水周圍的裝飾建材、美術品展示用保護玻璃、櫥窗、展示櫃、相框用蓋子、手錶、汽車窗用玻璃、列車、航空機等之窗玻璃、汽車頭燈、尾燈等之透明的玻璃製或透明的塑膠製(丙烯酸、聚碳酸酯等)構件、各種鏡子構件等之塗裝膜及表面保護膜有用。 As such items, such as tablet computers, mobile phones. Mobile (communication) information terminals, notebook computers, digital media players, phenotypes such as smart phones. Glasses-type wearable computers, digital cameras, digital cameras, e-book readers, etc., the frames of various machines that are held by humans to walk; liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes ( VFD), field emission projection display, CRT, toner display (toner display) and other flat panel displays and TV screens, etc. to indicate the surface of the operating machine, the exterior of the car, the glossy surface of the piano or furniture, the building of marble, etc. Decorative building materials around water used in stone surfaces, toilets, bathrooms, washrooms, etc., protective glass for art display, showcases, display cabinets, covers for photo frames, watches, car window glass, window glass for trains, aircraft, etc., and automobiles It is useful for coating films and surface protection films for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as headlights and taillights, and various mirror components.
尤其是具有以觸控面板顯示器等人之指或手 掌進行畫面上之操作的顯示輸入裝置之各種機器,例如作為平板型電腦、筆記型電腦、錶型穿戴式電腦、活動量計、手機.智慧型手機等移動(通信)的信息終端、數位媒體播放裝置、電子圖書閱讀器、數位相框、遊戲機及遊戲機之控制器、數位相機、數位攝影機、汽車用等之導航裝置、自動現金存取裝置、現金自動付款機、自動販賣機、數位看板(電子看板)、安全系統終端、POS終端、遙控器等各種控制器、車載裝置用面板開關等之顯示輸入裝置等之表面保護膜有用。 Especially with a touch panel display and other human fingers or hands Various machines of display and input devices that perform operations on the screen, such as tablet computers, notebook computers, wearable computers, activity meters, and mobile phones. Mobile (communication) information terminals such as smartphones, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital cameras, navigation devices for automobiles, etc., automatic cash deposits It is useful for the surface protection film of various controllers such as pick-up devices, cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controls, and display input devices such as panel switches for in-vehicle devices.
進而,藉由本發明之含氟活性能量線硬化性組成物所形成之硬化被膜作為光磁氣碟、光碟等之光學記錄媒介;眼鏡鏡片、照相機鏡頭、投影機鏡頭稜鏡、透鏡片、防護薄膜、偏光板、光學濾光器、雙凸透鏡、菲涅耳透鏡、防反射膜、光學纖維和光耦合器等之作為光學零件.光裝置的表面保護被膜或此等機器的各種保護零件的表面保護膜亦有用。 Furthermore, the cured film formed by the fluorine-containing active energy ray curable composition of the present invention is used as an optical recording medium for magneto-optical discs, optical discs, etc.; eyeglass lenses, camera lenses, projector lenses, lens sheets, protective films , Polarizing plate, optical filter, biconvex lens, Fresnel lens, anti-reflection film, optical fiber and optical coupler as optical parts. The surface protective film of the optical device or the surface protective film of various protective parts of such equipment is also useful.
以下雖表示合成例、實施例及比較例,具體說明本發明,但本發明並非被限定於下述之實施例。 Although synthesis examples, examples, and comparative examples are shown below to specifically describe the present invention, the present invention is not limited to the following examples.
於乾燥氮環境下具備迴流裝置與攪拌裝置之2,000mL三口燒瓶,投入下述式 CH2=CH-CH2-O-CH2-Rf’-CH2-O-CH2-CH=CH2 A 2,000 mL three-necked flask equipped with a reflux device and a stirring device in a dry nitrogen environment is put into the following formula CH 2 =CH-CH 2 -O-CH 2 -Rf'-CH 2 -O-CH 2 -CH=CH 2
Rf’:-CF2O(CF2O)p1(CF2CF2O)q1CF2- Rf': -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2-
(q1/p1=0.9、p1+q1≒45) (q1/p1=0.9, p1+q1≒45)
表示之全氟聚醚500g(0.125莫耳)、與六氟化間二甲苯700g、及四甲基環四矽氧烷361g(1.50莫耳),邊攪拌邊加熱至90℃。於此投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.442g(含有1.1×10-6莫耳作為Pt單體),將內溫維持在90℃以上直接持續攪拌4小時。以1H-NMR確認原料之烯丙基消失後,減壓餾除溶劑與過剩之四甲基環四矽氧烷。然後進行活性碳處理,而得到下述式表示之無色透明之液狀化合物(I)498g。 The indicated perfluoropolyether 500g (0.125 mol), 700g of m-xylene hexafluoride, and 361g (1.50 mol) of tetramethylcyclotetrasiloxane are heated to 90°C while stirring. Put here 0.442g of toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 -6 mol as Pt monomer), and maintain the internal temperature at 90°C Continue stirring directly for 4 hours. After confirming the disappearance of the allyl group of the raw material by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (I) represented by the following formula.
Rf’:-CF2O(CF2O)p1(CF2CF2O)q1CF2- Rf': -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2-
(q1/p1=0.9、p1+q1≒45) (q1/p1=0.9, p1+q1≒45)
於乾燥空氣環境下,相對於上述所得之化合物(I)200.0g(Si-H基量0.133莫耳),混合2-烯丙氧基乙醇28.20g(0.276莫耳)、六氟化間二甲苯200.0g、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液0.0884g(含有2.2×10-7莫耳作為Pt單體),於100℃攪拌4小時。以1H-NMR及IR確認Si-H基消失後,減壓餾除溶劑與過剩之2-烯丙氧基乙醇,進 行活性碳處理,而得到下述式表示之淡黃色透明之液體含氟醇化合物(C-1)216.1g。 In a dry air environment, with respect to 200.0 g of the compound (I) obtained above (Si-H group amount 0.133 mol), 28.20 g (0.276 mol) of 2-allyloxyethanol and m-xylene hexafluoride were mixed 200.0 g, and 0.0884 g of toluene solution of chloroplatinic acid/vinylsiloxane complex compound (containing 2.2×10 -7 mol as Pt monomer), and stirred at 100° C. for 4 hours. After confirming the disappearance of Si-H groups by 1 H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain a light yellow transparent liquid containing fluorine expressed by the following formula 216.1 g of alcohol compound (C-1).
Rf’:-CF2O(CF2O)p1(CF2CF2O)q1CF2- Rf': -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2-
(q1/p1=0.9、p1+q1≒45) (q1/p1=0.9, p1+q1≒45)
於乾燥氮環境下,於具備迴流裝置與攪拌裝置之3,000mL三口燒瓶,投入下述式CH2=CH-CH2-O-CH2-Rf’-CH2-O-CH2-CH=CH2 In a dry nitrogen environment, put the following formula CH 2 =CH-CH 2 -O-CH 2 -Rf'-CH 2 -O-CH 2 -CH=CH into a 3,000 mL three-necked flask equipped with a reflux device and a stirring device 2
Rf’:-CF2O(CF2O)p2(CF2CF2O)q2CF2- Rf': -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2-
(q2/p2=1.2、p2+q2≒18.5) (q2/p2=1.2, p2+q2≒18.5)
表示之全氟聚醚500g(0.272莫耳)、與六氟化間二甲苯1,000g、及四甲基環四矽氧烷660g(2.72莫耳),邊攪拌邊加熱至90℃。於此投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.884g(含有2.2×10-6莫耳作為Pt單體),將內溫維持在90℃以上直接持續攪拌4小時。以1H-NMR確認原料之烯丙基消失後,減壓餾除溶劑與過剩之四甲基環四矽氧烷。然後進行活性碳處理,而得到下述式表示之無色透明之液狀化合物(II)581g。 The indicated perfluoropolyether 500g (0.272 mol), 1,000 g of m-xylene hexafluoride, and 660 g (2.72 mol) of tetramethylcyclotetrasiloxane are heated to 90°C while stirring. Put 0.884 g of toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex here (containing 2.2×10 -6 mol as Pt monomer), and maintain the internal temperature at 90°C Continue stirring directly for 4 hours. After confirming the disappearance of the allyl group of the raw material by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 581 g of a colorless and transparent liquid compound (II) represented by the following formula.
Rf’:-CF2O(CF2O)p2(CF2CF2O)q2CF2- Rf': -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2-
(q2/p2=1.2、p2+q2≒18.5) (q2/p2=1.2, p2+q2≒18.5)
於乾燥空氣環境下,相對於上述所得之化合物(II)200.0g(Si-H基量0.518莫耳),混合2-烯丙氧基乙醇105.8g(1.04莫耳)、六氟化間二甲苯400.0g、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.77g(含有4.4×10-7莫耳作為Pt單體),於100℃攪拌4小時。以1H-NMR及IR確認Si-H基消失後,減壓餾除溶劑與過剩之2-烯丙氧基乙醇,進行活性碳處理,而得到下述式表示之淡黃色透明之液體含氟醇化合物(C-2)240.4g。 In a dry air environment, with respect to 200.0 g of the compound (II) obtained above (the amount of Si-H group is 0.518 mol), 105.8 g (1.04 mol) of 2-allyloxyethanol and m-xylene hexafluoride are mixed 400.0 g, and 1.77 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 4.4×10 -7 mol as Pt monomer), and stirred at 100°C for 4 hours. After confirming the disappearance of Si-H groups by 1 H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain a light yellow transparent liquid containing fluorine expressed by the following formula Alcohol compound (C-2) 240.4g.
Rf’:-CF2O(CF2O)p2(CF2CF2O)q2CF2- Rf': -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2-
(q2/p2=1.2、p2+q2≒18.5) (q2/p2=1.2, p2+q2≒18.5)
於乾燥空氣環境下,相對於合成例1所得之含氟醇化 合物(C-1)50.0g(羥基量0.058莫耳),混合(B-1)2-(全氟己基)乙基丙烯酸酯[黏度4mPa.s/25℃]57.9g、(D)丙烯醯氧基乙基異氰酸酯7.87g(0.055莫耳),加熱至50℃攪拌1小時。對其添加二辛基錫(二)月桂酸酯0.05g,50℃下攪拌8小時。從1H-NMR的結果,確認未反應之丙烯醯氧基乙基異氰酸酯的4.2ppm之亞甲基峰值,對胺基甲酸乙酯鍵形成後之4.1ppm的亞甲基峰值全部改變,又,從IR光譜確認2,260cm-1之異氰酸酯基之峰值的消失。加熱結束後,於所得之反應液進行活性碳處理,而得到淡黃色液體100.3g。藉此,得到(C-1)與(D)的反應物即下述所示之含氟丙烯酸化合物(A-1)與2-(全氟己基)乙基丙烯酸酯(B-1)以(A-1)/(B-1)=1的質量比率混合之含氟丙烯酸組成物(F-1)。 In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), (B-1) 2-(perfluorohexyl) ethyl acrylate [ Viscosity 4mPa. s/25°C] 57.9 g, (D) 7.87 g (0.055 mol) of propylene oxyethyl isocyanate, heated to 50°C and stirred for 1 hour. 0.05 g of dioctyltin (di)laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm -1 disappeared. After the heating, the resultant reaction liquid was treated with activated carbon to obtain 100.3 g of light yellow liquid. Thereby, the reactants of (C-1) and (D), namely the fluorinated acrylic compound (A-1) shown below and 2-(perfluorohexyl)ethyl acrylate (B-1), are obtained ( A fluorinated acrylic composition (F-1) mixed with a mass ratio of A-1)/(B-1)=1.
Rf’:-CF2O(CF2O)p1(CF2CF2O)q1CF2- Rf': -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2-
(q1/p1=0.9、p1+q1≒45) (q1/p1=0.9, p1+q1≒45)
於乾燥空氣環境下,相對於合成例1所得之含氟醇化 合物(C-1)50.0g(羥基量0.058莫耳),混合(B-2)2-(全氟己基)乙基甲基丙烯酸酯[黏度5mPa.s/25℃]57.9g、(B-3)異丁基丙烯酸酯[黏度1mPa.s/25℃]115.8g、(D)丙烯醯氧基乙基異氰酸酯7.87g(0.055莫耳),加熱至50℃攪拌1小時。對其添加錫(二)月桂酸酯0.05g,50℃下攪拌8小時。從1H-NMR的結果,確認未反應之丙烯醯氧基乙基異氰酸酯的4.2ppm之亞甲基峰值,對胺基甲酸乙酯鍵形成後之4.1ppm的亞甲基峰值全部改變,又,從IR光譜確認2,260cm-1之異氰酸酯基之峰值的消失。加熱結束後,於所得之反應液進行活性碳處理,而得到淡黃色液體170.1g。藉此,得到由(C-1)與(D)的反應物即下述所示之含氟丙烯酸化合物(A-1)與2-(全氟己基)乙基甲基丙烯酸酯(B-2)及異丁基丙烯酸酯(B-3)所構成,(A-1)/[(B-2)+(B-3)]=0.33的質量比率之含氟丙烯酸組成物(F-2)。 In a dry air environment, with respect to 50.0 g of the fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), mix (B-2) 2-(perfluorohexyl) ethyl methacrylic acid Ester [viscosity 5mPa. s/25℃] 57.9g, (B-3) isobutyl acrylate [viscosity 1mPa. s/25°C] 115.8 g, (D) 7.87 g (0.055 mol) of acryloxyethyl isocyanate, heated to 50°C and stirred for 1 hour. 0.05 g of tin (two) laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm -1 disappeared. After heating, the resultant reaction liquid was treated with activated carbon to obtain 170.1 g of light yellow liquid. Thereby, the reactants of (C-1) and (D), namely the fluorinated acrylic compound (A-1) and 2-(perfluorohexyl)ethyl methacrylate (B-2) shown below, are obtained. ) And isobutyl acrylate (B-3), a fluorinated acrylic composition (F-2) with a mass ratio of (A-1)/[(B-2)+(B-3)]=0.33 .
於乾燥空氣環境下,相對於合成例1所得之含氟醇化合物(C-1)50.0g(羥基量0.058莫耳),混合六氟化間二甲苯50.0g、(D)丙烯醯氧基乙基異氰酸酯7.87g(0.055莫耳),加熱至50℃攪拌1小時。對其添加錫(二)月桂酸酯0.05g,50℃下攪拌8小時。從1H-NMR的結果,確認未反應之丙烯醯氧基乙基異氰酸酯的4.2ppm之亞甲基峰值,對胺基甲酸乙酯鍵形成後之4.1ppm的亞甲基峰值全部改變,又,從IR光譜確認2,260cm-1之異氰酸酯基之峰值的消失而結束加熱。 於所得之反應液進行活性碳處理,而得到淡黃色液體98.2g。將所得之淡黃色液體以旋轉蒸發器於60℃、133.32Pa進行減壓餾除3小時,單離(A-1)作為55.2g之淡黃色軟膏狀成分。確認所得之(A-1)以105℃、3小時之加熱乾燥質量減少為0.01質量%以下。 In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), 50.0 g of m-xylene hexafluoride and (D) propylene oxyethyl are mixed 7.87 g (0.055 mol) of methyl isocyanate was heated to 50°C and stirred for 1 hour. 0.05 g of tin (two) laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm -1 disappeared, and the heating was terminated. The resultant reaction liquid was treated with activated carbon to obtain 98.2 g of a pale yellow liquid. The obtained light yellow liquid was distilled off under reduced pressure with a rotary evaporator at 60° C. and 133.32 Pa for 3 hours, and (A-1) was isolated as a light yellow ointment component of 55.2 g. It was confirmed that the mass of (A-1) obtained after heating and drying at 105°C for 3 hours was reduced to 0.01% by mass or less.
將於上述所得之(A-1)10g置入附蓋之玻璃的瓶體容器,加入(B-4)2-(全氟丁基)乙基丙烯酸酯[黏度3mPa.s/25℃]10g、(B-5)四氫呋喃基丙烯酸酯[黏度3mPa.s/25℃]30g,以振動機振動至均一溶解為止,而得到(A-1)/[(B-4)+(B-5)]=0.25之質量比率之含氟丙烯酸組成物(F-3)。 Put 10g of (A-1) obtained above into a glass bottle container with a lid, and add (B-4) 2-(perfluorobutyl) ethyl acrylate [viscosity 3mPa. s/25℃] 10g, (B-5) tetrahydrofuryl acrylate [viscosity 3mPa. s/25℃] 30g, vibrate with a vibrator until uniformly dissolved, and obtain a fluorinated acrylic composition (F) with a mass ratio of (A-1)/[(B-4)+(B-5)]=0.25 -3).
於乾燥空氣環境下,相對於合成例2所得之含氟醇化合物(C-2)50.0g(羥基量0.102莫耳),混合(B-3)異丁基丙烯酸酯254.8g、(D)丙烯醯氧基乙基異氰酸酯13.7g(0.097莫耳),加熱至50℃攪拌1小時。對其添加二辛基錫(二)月桂酸酯0.10g,50℃下攪拌8小時。從1H-NMR的結果,確認未反應之丙烯醯氧基乙基異氰酸酯的4.2ppm之亞甲基峰值,對胺基甲酸乙酯鍵形成後之4.1ppm的亞甲基峰值全部改變,又,從IR光譜確認2,260cm-1之異氰酸酯基之峰值的消失。加熱結束後,於所得之反應液進行活性碳處理,而得到淡黃色液體318.7g。藉此,得到由(C-2)與(D)的反應物即下述所示之含氟丙烯酸化合物(A-2)與(B-3)異丁基丙 烯酸酯以(A-2)/(B-3)=0.25之質量比率混合之含氟丙烯酸組成物(F-4)。 In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-2) obtained in Synthesis Example 2 (amount of hydroxyl group: 0.102 mol), 254.8 g of (B-3) isobutyl acrylate and (D) propylene were mixed 13.7 g (0.097 mol) of oxyethyl isocyanate was heated to 50°C and stirred for 1 hour. 0.10 g of dioctyltin (di)laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of 1 H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm -1 disappeared. After the heating, the resultant reaction liquid was treated with activated carbon to obtain 318.7 g of light yellow liquid. Thereby, the reactants of (C-2) and (D), namely the fluorine-containing acrylic compound (A-2) and (B-3) isobutyl acrylate shown below, are obtained with (A-2)/ (B-3) = A fluorine-containing acrylic composition (F-4) mixed with a mass ratio of 0.25.
Rf’:-CF2O(CF2O)p2(CF2CF2O)q2CF2- Rf': -CF 2 O(CF 2 O) p2 (CF 2 CF 2 O) q2 CF 2-
(q2/p2=1.2、p2+q2≒18.5) (q2/p2=1.2, p2+q2≒18.5)
尚,於上述實施例1~4所得之含氟丙烯酸組成物未包含揮發性有機化合物。 Furthermore, the fluorine-containing acrylic composition obtained in the foregoing Examples 1 to 4 does not contain volatile organic compounds.
在實施例3,雖替換成(B-5)四氫呋喃基丙烯酸酯,使用3官能丙烯酸化合物之三羥甲基丙烷三丙烯酸酯[黏度110mPa.s/25℃]嘗試組成物的調製,但未溶解而分離。 In Example 3, although (B-5) tetrahydrofuryl acrylate was replaced, trimethylolpropane triacrylate, a trifunctional acrylic compound, was used [viscosity 110mPa. s/25°C] Tried preparation of the composition, but separated without dissolving.
使用以下之丙烯酸化合物(Ea)及光聚合起始劑(Eb),調製活性能量線硬化性組成物(E)。 The following acrylic compound (Ea) and photopolymerization initiator (Eb) were used to prepare an active energy ray curable composition (E).
[新中村化學股份有限公司製A-9550] [A-9550 manufactured by Shinnakamura Chemical Co., Ltd.]
[新中村化學股份有限公司製A-TMM-3] [A-TMM-3 manufactured by Shinnakamura Chemical Co., Ltd.]
[Daicel ornex股份有限公司製EBECRYL 40] [EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.]
[BASF日本股份有限公司製IRGACURE 184] [IRGACURE 184 manufactured by BASF Japan Co., Ltd.]
[BASF日本股份有限公司製IRGACURE 127] [IRGACURE 127 manufactured by BASF Japan Co., Ltd.]
活性能量線硬化性組成物(E1): Active energy ray hardening composition (E1):
(Ea-1)70質量份 (Ea-1) 70 parts by mass
(Ea-4)30質量份 (Ea-4) 30 parts by mass
(Eb-1)3質量份 (Eb-1) 3 parts by mass
活性能量線硬化性組成物(E2): Active energy ray hardening composition (E2):
(Ea-1)70質量份 (Ea-1) 70 parts by mass
(Ea-2)30質量份 (Ea-2) 30 parts by mass
(Eb-1)3質量份 (Eb-1) 3 parts by mass
活性能量線硬化性組成物(E3): Active energy ray hardening composition (E3):
(Ea-1)30質量份 (Ea-1) 30 parts by mass
(Ea-2)70質量份 (Ea-2) 70 parts by mass
(Eb-1)3質量份 (Eb-1) 3 parts by mass
活性能量線硬化性組成物(E4): Active energy ray curable composition (E4):
(Ea-3)100質量份 (Ea-3) 100 parts by mass
(Eb-2)3質量份 (Eb-2) 3 parts by mass
又,將比較用組成物(G-1)、(G-2)用以下之比率調製。 In addition, the comparative compositions (G-1) and (G-2) were prepared with the following ratios.
(G-1):(B-1)50質量份、(B-2)100質量份 (G-1): (B-1) 50 parts by mass, (B-2) 100 parts by mass
(G-2):(B-1)50質量份、(B-2)150質量份 (G-2): (B-1) 50 parts by mass, (B-2) 150 parts by mass
以下述表1所示之摻合比例,混合上述實施例所得之含氟丙烯酸組成物(F-1)~(F-4)、上述含氟丙烯酸化合物(A-1)、2-(全氟己基)乙基丙烯酸酯(B-1)或上述比較用組成物(G-1)、(G-2)、及上述活性能量線硬化性組成物(E1)~(E4),調製含氟活性能量線硬化性組成物。測定所得之組成物的外觀並示於表1。 Mix the fluorinated acrylic composition (F-1)~(F-4) obtained in the above example, the above fluorinated acrylic compound (A-1), 2-(perfluoroacrylic acid compound) at the blending ratio shown in Table 1 below. Hexyl) ethyl acrylate (B-1) or the above-mentioned comparative composition (G-1), (G-2), and the above-mentioned active energy ray curable composition (E1) to (E4) to prepare fluorine-containing activity Energy ray curable composition. The appearance of the obtained composition was measured and shown in Table 1.
將實施例及比較例之各含氟活性能量線硬化性組成物以旋塗塗佈於碳酸酯基板上。塗佈後,於室溫整平10分鐘後,使用輸送帶式金屬鹵化物UV照射裝置(Panasonic電工製),於氮環境中,將積算照射量1,600mJ/cm2之紫外線照射在塗佈面,使組成物硬化,而得到厚度9μm之硬化膜。針對實施例10,取代於室溫整平10分鐘,改以100℃進行1分鐘加熱。 Each fluorine-containing active energy ray curable composition of the Examples and Comparative Examples was applied on the carbonate substrate by spin coating. After coating, after leveling at room temperature for 10 minutes, use a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works) to irradiate the coated surface with a cumulative amount of 1,600mJ/cm 2 of ultraviolet radiation in a nitrogen environment , The composition is cured to obtain a cured film with a thickness of 9μm. For Example 10, instead of flattening at room temperature for 10 minutes, heating was performed at 100°C for 1 minute.
在目視測定上述所得之硬化膜的外觀(透明性),同時藉由下述所示之方法進行水接觸角之測定及耐油性簽字性的評估。將此等之結果示於表1。 The appearance (transparency) of the cured film obtained above was visually measured, and at the same time, the measurement of the water contact angle and the evaluation of the oil resistance signature were performed by the method shown below. The results are shown in Table 1.
使用接觸角計(協和界面科學股份有限公司製DropMaster),將2μL之液滴滴下於硬化膜上,測定1秒後之接觸角。將N=5之平均值作為測定值。 Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL drop was dropped on the cured film, and the contact angle after 1 second was measured. Take the average value of N=5 as the measured value.
於硬化膜表面以油性簽字筆(寺西化學工業股份有限公司製 萬能墨水大型)描繪直線,將排斥墨者定為○,未排斥者定為×。 On the surface of the hardened film, draw a straight line with an oil-based pen (manufactured by Sisei Chemical Industry Co., Ltd., universal ink large-scale), and mark those who reject ink as ○ and those who do not reject it as ×.
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CN107298751B (en) | 2021-10-26 |
TW201806992A (en) | 2018-03-01 |
CN107298751A (en) | 2017-10-27 |
JP2017190429A (en) | 2017-10-19 |
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JP6497350B2 (en) | 2019-04-10 |
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