JP5012005B2 - Fluorine-containing composition and fluorine-containing polyfunctional thiol - Google Patents
Fluorine-containing composition and fluorine-containing polyfunctional thiol Download PDFInfo
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- JP5012005B2 JP5012005B2 JP2006351706A JP2006351706A JP5012005B2 JP 5012005 B2 JP5012005 B2 JP 5012005B2 JP 2006351706 A JP2006351706 A JP 2006351706A JP 2006351706 A JP2006351706 A JP 2006351706A JP 5012005 B2 JP5012005 B2 JP 5012005B2
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- Prior art keywords
- fluorine
- compound
- group
- acrylate
- composition
- Prior art date
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 141
- 239000011737 fluorine Substances 0.000 title claims abstract description 119
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 125000003396 thiol group Chemical class [H]S* 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- -1 thiol compound Chemical class 0.000 claims abstract description 32
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 7
- 150000003573 thiols Chemical class 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- NOEMSRWQFGPZQS-UHFFFAOYSA-N CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO Chemical compound CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO NOEMSRWQFGPZQS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- XVKLLVZBGMGICC-UHFFFAOYSA-N o-[3-propanethioyloxy-2,2-bis(propanethioyloxymethyl)propyl] propanethioate Chemical compound CCC(=S)OCC(COC(=S)CC)(COC(=S)CC)COC(=S)CC XVKLLVZBGMGICC-UHFFFAOYSA-N 0.000 claims description 3
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical group OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 claims description 2
- WBEKRAXYEBAHQF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.CCC(CO)(CO)CO WBEKRAXYEBAHQF-UHFFFAOYSA-N 0.000 claims description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 2
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 33
- 239000011521 glass Substances 0.000 abstract description 31
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 28
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 50
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000035807 sensation Effects 0.000 description 12
- 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 11
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 11
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 11
- 229910001507 metal halide Inorganic materials 0.000 description 11
- 150000005309 metal halides Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- OVQQQQUJAGEBHH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)OC(=O)C=C OVQQQQUJAGEBHH-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000105 evaporative light scattering detection Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- TXZNVWGSLKSTDH-XCADPSHZSA-N (1Z,3Z,5Z)-cyclodeca-1,3,5-triene Chemical class C1CC\C=C/C=C\C=C/C1 TXZNVWGSLKSTDH-XCADPSHZSA-N 0.000 description 1
- WVLCUUANGIHRLK-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecane-1-thiol Chemical compound FC(F)(F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S WVLCUUANGIHRLK-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- NLOCXQZOOGBEEN-UHFFFAOYSA-N 1-(1-hydroxypropan-2-yloxy)-3-phenoxypropan-2-ol Chemical compound OCC(C)OCC(O)COC1=CC=CC=C1 NLOCXQZOOGBEEN-UHFFFAOYSA-N 0.000 description 1
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- WQHNZXURJISVCT-UHFFFAOYSA-N 1-butoxyethane-1,2-diol Chemical compound CCCCOC(O)CO WQHNZXURJISVCT-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-piperidin-4-yloxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCNCC1 ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- LKYFXAKMDQISTA-UHFFFAOYSA-N FC(C(C(C(C(C(C(C(C(C(C(F)(F)OC(C=C)=O)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(CCC(F)(F)F)F Chemical compound FC(C(C(C(C(C(C(C(C(C(C(F)(F)OC(C=C)=O)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(CCC(F)(F)F)F LKYFXAKMDQISTA-UHFFFAOYSA-N 0.000 description 1
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- VCFFZAQQHCLMNH-UHFFFAOYSA-N [3-(6-prop-2-enoyloxyhexanoyloxy)-2-[[3-(6-prop-2-enoyloxyhexanoyloxy)-2,2-bis(6-prop-2-enoyloxyhexanoyloxymethyl)propoxy]methyl]-2-(6-prop-2-enoyloxyhexanoyloxymethyl)propyl] 6-prop-2-enoyloxyhexanoate Chemical compound C=CC(=O)OCCCCCC(=O)OCC(COC(=O)CCCCCOC(=O)C=C)(COC(=O)CCCCCOC(=O)C=C)COCC(COC(=O)CCCCCOC(=O)C=C)(COC(=O)CCCCCOC(=O)C=C)COC(=O)CCCCCOC(=O)C=C VCFFZAQQHCLMNH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- HIVQCJOGAHNXBO-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C HIVQCJOGAHNXBO-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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Abstract
Description
本発明は、各種基材、特にガラスへの密着性が良好な含フッ素組成物、並びに、新規含フッ素多官能チオールに関する。 The present invention relates to a fluorine-containing composition having good adhesion to various substrates, particularly glass, and a novel fluorine-containing polyfunctional thiol.
含フッ素高分子化合物は、化学的安定性、光学特性、屈折率、透明性、撥水撥油性などの特長を有することから、産業上、広く利用されている。しかしながら、ガラスをはじめとする各種基材への密着性が悪いという欠点を有する。この欠点を克服すべく、特にガラス基材に対する密着性向上の試みは、以前より種々の方法により行なわれている。 Fluorine-containing polymer compounds are widely used in industry because they have features such as chemical stability, optical properties, refractive index, transparency, and water / oil repellency. However, it has a drawback that adhesion to various substrates such as glass is poor. In order to overcome this drawback, attempts to improve adhesion particularly to glass substrates have been made by various methods.
ガラス基材をシランカップリング剤により前処理し、ガラス基材の表面に有機化合物と密着性が良好な層を作成する方法が一般的に行なわれている。しかしながら、この方法ではシランカップリング処理の工程が増えて、煩雑となり、不利である。工程数の増加を伴わぬよう、シランカップリング剤を含フッ素組成物に添加し、このものをガラス基材上で硬化する方法も提案されているが、この方法では組成物のポットライフが短くなる難点がある。 In general, a method of pretreating a glass substrate with a silane coupling agent to form a layer having good adhesion to an organic compound on the surface of the glass substrate is performed. However, this method is disadvantageous because it increases the number of silane coupling treatment steps, which is complicated. A method of adding a silane coupling agent to a fluorine-containing composition and curing it on a glass substrate has been proposed so as not to increase the number of steps, but this method shortens the pot life of the composition. There is a difficult point.
また、組成物にチオール化合物を導入し、密着性を向上させる検討も行なわれているが（例えば、特許文献１参照。）、一般的なチオール化合物を含フッ素組成物へ導入しようとすると、著しい硬化性の低下を引き起こしたり、あるいは相溶性が悪く、成膜や成形加工後の塗膜が白濁したりして、目的とする透明性が損なわれる。さらに、チオール化合物は一般的に屈折率が高いため、組成物中に存在すると、含フッ素高分子化合物の特長である低屈折率性を発現できなくなる。このため、更なる改善が求められている。 In addition, studies have been made to improve the adhesion by introducing a thiol compound into the composition (see, for example, Patent Document 1). However, when a general thiol compound is to be introduced into a fluorine-containing composition, it is remarkable. Decrease in curability or poor compatibility, and the coating film after film formation or molding becomes cloudy, and the target transparency is impaired. Furthermore, since the thiol compound generally has a high refractive index, when it exists in the composition, the low refractive index property that is a feature of the fluorine-containing polymer compound cannot be expressed. For this reason, further improvement is required.
一方、金属用防錆剤として含フッ素チオール化合物が提案されているが（特許文献２参照。）、特定の構造を有する含フッ素チオール化合物を硬化性組成物に利用可能か否か、また含フッ素チオール化合物が基材に対する密着性に寄与するか否か検討している例は未だかつてなく、該特許明細書中に記載されている唯一の含フッ素二官能チオールは、含フッ素組成物に対する溶解性が不良であるトリアジン骨格を有するため、このものを含フッ素組成物へ導入すると目的とする透明性が損なわれる。 On the other hand, although a fluorine-containing thiol compound has been proposed as a metal rust preventive (see Patent Document 2), whether or not a fluorine-containing thiol compound having a specific structure can be used for a curable composition, and fluorine-containing There has never been an example in which whether a thiol compound contributes to adhesion to a substrate, and the only fluorine-containing bifunctional thiol described in the patent specification is soluble in fluorine-containing compositions. Therefore, when this is introduced into a fluorine-containing composition, the intended transparency is impaired.
上記のような実情に鑑み、本発明の課題は、基材、特にガラス基材への密着性が良好であり、且つ硬化後に透明な硬化物を与える含フッ素組成物、ならびに上記密着性発現に必要となる新規含フッ素多官能チオール化合物を提供することにある。 In view of the above circumstances, the object of the present invention is to provide a fluorine-containing composition that has good adhesion to a substrate, particularly a glass substrate, and gives a transparent cured product after curing, and the above-described adhesion expression. The object is to provide a novel fluorine-containing polyfunctional thiol compound which is necessary.
本発明者は、上記課題を解決するために鋭意検討したところ、新規に合成した含フッ素多官能チオールを、含フッ素組成物中に配合することにより、硬化後も透明性を損なうことなく、ガラス基材への密着性を向上させることを見出し、本発明を完成した。 The present inventor has intensively studied to solve the above-mentioned problems. As a result, the newly synthesized fluorine-containing polyfunctional thiol is blended in the fluorine-containing composition, so that the glass is not impaired even after curing. The inventors have found that the adhesion to the substrate is improved and completed the present invention.
即ち、本発明は、下記一般式（Ｉ）で表わされる含フッ素α，β−不飽和カルボニル化合物（Ｘ）と１分子中に３個以上のメルカプト基を有する化合物（Ｙ）とを反応させて得られる含フッ素多官能チオール（Ｂ）であり、１分子中に３個以上のメルカプト基を有する化合物（Ｙ）が、下記一般式（ＩＩ）〜（ＩＶ）からなる群から選ばれる少なくとも一種の化合物である含フッ素多官能チオールを提供する。 That is, in the present invention, a fluorine-containing α, β-unsaturated carbonyl compound (X) represented by the following general formula (I) is reacted with a compound (Y) having three or more mercapto groups in one molecule. The obtained fluorine-containing polyfunctional thiol (B) , wherein the compound (Y) having three or more mercapto groups in one molecule is at least one selected from the group consisting of the following general formulas (II) to (IV) Provided is a fluorine-containing polyfunctional thiol which is a compound .
本発明によれば、フッ素原子含有量が高い含フッ素組成物であっても、硬化後に透明性を損なうことなく、ガラス基材への密着性に優れた硬化物を得ることができる。このことから、光学用途やハードコート剤用途等ガラス基材への密着性が要求される種々の用途に利用可能である。また、本発明の組成物は、一般的に用いられるようなシランカップリング剤を配合した組成物に比べてポットライフが長く、工業的有用性が高い。 According to this invention, even if it is a fluorine-containing composition with high fluorine atom content, the hardened | cured material excellent in the adhesiveness to a glass base material can be obtained, without impairing transparency after hardening. From this, it can utilize for the various use as which the adhesiveness to a glass substrate is requested | required, such as an optical use and a hard-coat agent use. In addition, the composition of the present invention has a long pot life and high industrial utility compared to a composition containing a silane coupling agent that is generally used.
本発明で用いる含フッ素組成物（Ａ）は、フッ素原子含有量が組成物中に２０重量％以上である含フッ素組成物を表わす。本発明の組成物中において組成物の成膜性ならびに透明性、低屈折率性、低反射率性等の光学特性および柔軟性、硬度等の力学特性、低誘電率性、絶縁性等の電気特性、さらに耐光性、耐薬品性、低吸水性を付与する、極めて重要な成分である。フッ素原子含有量が２０重量％以上であれば、制限なく用いることができるが、上限としては、７０重量％以下が好ましい。硬化物の光学特性と力学物性のバランスを考慮すると、より好ましい範囲は２０重量％以上６０重量％以下であり、２２重量％以上５７重量％以下が特に好ましい。 The fluorine-containing composition (A) used in the present invention represents a fluorine-containing composition having a fluorine atom content of 20% by weight or more in the composition. In the composition of the present invention, the film-forming property of the composition, optical properties such as transparency, low refractive index properties, low reflectance properties, and flexibility, mechanical properties such as hardness, electrical properties such as low dielectric constant, insulating properties, etc. It is an extremely important component that imparts properties, light resistance, chemical resistance, and low water absorption. If the fluorine atom content is 20% by weight or more, it can be used without limitation, but the upper limit is preferably 70% by weight or less. In consideration of the balance between optical properties and mechanical properties of the cured product, a more preferable range is 20 wt% or more and 60 wt% or less, and 22 wt% or more and 57 wt% or less is particularly preferable.
本発明において用いるフッ素原子含有量が２０重量％以上である含フッ素組成物（Ａ）は、特に制限なく用いることができるが、該組成物を紫外線にて迅速に硬化させる際には、エチレン性不飽和単量体を含有させることが好ましく、更に、他の成分との相溶性が良好で、硬化物の透明性が優れることから、特に、（メタ）アクリロイル基を含有する化合物を該組成物中の２０重量％以上含有する硬化性組成物とすることが好ましい。（メタ）アクリロイル基を含有する化合物を２０重量％以上含有する硬化性組成物の構成成分としては、含フッ素重合性単量体（Ａ１）及び／又は含フッ素重合体（Ａ２）等が例示可能であるが、これによって特に制限されるものではない。 The fluorine-containing composition (A) having a fluorine atom content of 20% by weight or more used in the present invention can be used without particular limitation, but when the composition is rapidly cured with ultraviolet rays, it is ethylenic. It is preferable to contain an unsaturated monomer, and since the compatibility with other components is good and the transparency of the cured product is excellent, in particular, a compound containing a (meth) acryloyl group is used in the composition. It is preferable to use a curable composition containing 20% by weight or more. Examples of constituents of the curable composition containing 20% by weight or more of a compound containing a (meth) acryloyl group include a fluorine-containing polymerizable monomer (A1) and / or a fluorine-containing polymer (A2). However, it is not particularly limited by this.
含フッ素重合性単量体（Ａ１）を例示するならば、原料の入手容易性、及び組成物中の他の成分との相溶性が良好である等の観点から、下記一般式（ａ１）にて表されるフッ素化（メタ）アクリレートを用いることが好ましい。 If the fluorine-containing polymerizable monomer (A1) is exemplified, the following general formula (a1) is used from the viewpoint of easy availability of raw materials and good compatibility with other components in the composition. It is preferable to use a fluorinated (meth) acrylate represented by
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯ（Ｘ）ａＲｆ・・・・・・（ａ１）
〔式（１）中、Ｒ１は水素原子、メチル基、塩素原子、フッ素原子又はシアノ基であり、Ｘはフッ素原子を含まない２価の連結基であり、ａは０又は１の整数であり、Ｒｆは炭素数１〜２０のパーフルオロアルキル基、または−（ＣＦ２）６Ｈ等の部分フッ素化アルキル基であって、直鎖状、分岐状、または主鎖中に酸素原子が介入したものでも良い。〕
CH 2 = C (R 1 ) COO (X) a Rf (a1)
[In Formula (1), R 1 is a hydrogen atom, a methyl group, a chlorine atom, a fluorine atom or a cyano group, X is a divalent linking group containing no fluorine atom, and a is an integer of 0 or 1. Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group such as — (CF 2 ) 6 H, which is linear, branched, or intervened with an oxygen atom in the main chain What you did is fine. ]
前記一般式（ａ１）中の２価の連結基Ｘとしては、例えば、−（ＣＨ２）ｎ−、−ＣＨ２ＣＨ（ＯＨ）（ＣＨ２）ｎ−、−（ＣＨ２）ｎＮ（Ｒ２）ＳＯ２−、−（ＣＨ２）ｎＮ（Ｒ２）ＣＯ−（式中、ｎは１〜１０の整数であり、Ｒ２は水素原子又は炭素数１〜１８のアルキル基である。）、−ＣＨ（ＣＨ３）−、−ＣＨ（ＣＨ２ＣＨ３）−、−Ｃ（ＣＨ３）２−等の連結基が挙げられ、前記一般式（１）中のＲｆとしては、例えば、−Ｃ４Ｆ９、−Ｃ６Ｆ１３、−Ｃ７Ｆ１５、−Ｃ８Ｆ１７、−（ＣＦ２）４Ｈ、−（ＣＦ２）６ＣＦ（ＣＦ３）２、−（ＯＣＦ２ＣＦ２）４ＯＣＦ２ＣＦ３、−（ＯＣＦ２ＣＦ（ＣＦ３））３Ｃ３Ｆ７等のフッ素化アルキル基が挙げられるが、特に制限されるものではない。
Examples of the divalent linking group X in the general formula (a1) include — (CH 2 ) n —, —CH 2 CH (OH) (CH 2 ) n —, — (CH 2 ) n N (R 2) SO 2 -, - ( CH 2) n n (R 2) CO- ( wherein, n is an integer from 1 to 10, R 2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ), —CH (CH 3 ) —, —CH (CH 2 CH 3 ) —, —C (CH 3 ) 2 — and the like. Examples of Rf in the general formula (1) include: -C 4 F 9, -C 6 F 13, -C 7 F 15, -C 8 F 17, - (CF 2) 4 H, - (CF 2) 6 CF (CF 3) 2, - (OCF 2 CF 2) 4 OCF 2 CF 3, - (OCF 2 CF (CF 3)) 3
前記フッ素化（メタ）アクリレートとしては、以下の如き化合物が挙げられる。
Ａ１−１ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ８Ｆ１７
Ａ１−２ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ８Ｆ１７
Ａ１−３ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ１２Ｆ２５
Ａ１−４ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ１２Ｆ２５
Ａ１−５ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ６Ｆ１３
Ａ１−６ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ６Ｆ１３
Ａ１−７ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ４Ｆ９
Ａ１−８ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ４Ｆ９
Ａ１−９ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＦ３
Ａ１−１０：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＦ（ＣＦ３）２
Ａ１−１１：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＦＨＣＦ３
Ａ１−１２：ＣＨ２＝ＣＨＣＯＯＣＨ２（ＣＦ２）６Ｈ
Ａ１−１３：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｃ８Ｆ１７
Ａ１−１４：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｎ（Ｃ３Ｈ７）ＳＯ２Ｃ８Ｆ１７
Ａ１−１５：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｎ（Ｃ２Ｈ５）ＣＯＣ７Ｆ１５
Ａ１−１６：ＣＨ２＝ＣＨＣＯＯＣ２Ｈ４（ＣＦ（ＣＦ３）ＯＣＦ２）３Ｃ２Ｆ５
Ａ１−１７：ＣＨ２＝ＣＨＣＯＯＣＨ２（ＣＦ（ＣＦ３）ＯＣＦ２）２Ｃ２Ｆ５
Examples of the fluorinated (meth) acrylate include the following compounds.
A1-1: CH 2 = CHCOOCH 2 CH 2 C 8 F 17
A1-2: CH 2 = C (CH 3) COOCH 2 CH 2 C 8 F 17
A1-3: CH 2 = CHCOOCH 2 CH 2 C 12 F 25
A1-4: CH 2 = C (CH 3) COOCH 2 CH 2 C 12 F 25
A1-5: CH 2 = CHCOOCH 2 CH 2 C 6 F 13
A1-6: CH 2 = C (CH 3) COOCH 2 CH 2 C 6 F 13
A1-7: CH 2 = CHCOOCH 2 CH 2 C 4 F 9
A1-8: CH 2 = C (CH 3) COOCH 2 CH 2 C 4 F 9
A1-9: CH 2 = CHCOOCH 2 CF 3
A1-10: CH 2 = C (CH 3) COOCH 2 CF (CF 3) 2
A1-11: CH 2 = C (CH 3) COOCH 2
A1-12: CH 2 = CHCOOCH 2 ( CF 2) 6 H
A1-13: CH 2 = CHCOOCH 2 CH (OH) CH 2 C 8 F 17
A1-14: CH 2 = CHCOOCH 2 CH 2 N (C 3 H 7) SO 2 C 8 F 17
A1-15: CH 2 = CHCOOCH 2 CH 2 N (C 2 H 5) COC 7 F 15
A1-16: CH 2 = CHCOOC 2 H 4 (CF (CF 3) OCF 2) 3 C 2
A1-17: CH 2 = CHCOOCH 2 ( CF (CF 3) OCF 2) 2 C 2
なお、これら例示化合物によって本特許が何ら制限されるものではない。 In addition, this patent is not restrict | limited at all by these exemplary compounds.
次に含フッ素重合体（Ａ２）について述べる。含フッ素重合体（Ａ２）は、該組成物を低屈折率および透明性を目的とする塗布、成形作業性に合致した粘度に調整し、あるいは硬化物に使用目的に適した力学・光学特性を付与する場合に導入する成分であり、含フッ素重合性単量体（Ａ１）と良好に相溶する。含フッ素重合体（Ａ２）は重合体中にフッ素原子を含有してさえいればよく、含フッ素重合性単量体（Ａ１）中及び／又は含フッ素重合体（Ａ２）由来のフッ素原子の合計が含フッ素組成物（Ａ）中で２０重量％以上となるようなものであれば特に制限なく用いることができる。また、含フッ素重合体（Ａ２）は、反応性基を含有するものであっても、あるいは反応性基を含有していないものであっても構わない。 Next, the fluoropolymer (A2) will be described. The fluorine-containing polymer (A2) has a mechanical and optical property suitable for the intended use of the cured product by adjusting the composition to a viscosity that matches the coating and molding workability for the purpose of low refractive index and transparency. It is a component introduced in the case of imparting, and is well compatible with the fluorine-containing polymerizable monomer (A1). The fluorine-containing polymer (A2) only needs to contain fluorine atoms in the polymer, and the total of fluorine atoms derived from the fluorine-containing polymerizable monomer (A1) and / or the fluorine-containing polymer (A2). Can be used without particular limitation as long as it is 20% by weight or more in the fluorine-containing composition (A). Further, the fluoropolymer (A2) may contain a reactive group or may not contain a reactive group.
さらに、フッ素原子含有量が２０重量％以上である含フッ素組成物（Ａ）の構成成分として、非フッ素重合性単量体（Ａ３）あるいは非フッ素重合体（Ａ４）も例示することができる。非フッ素重合性単量体（Ａ３）は、分子中にフッ素原子を含まずに、アクリロイル基及び／又はメタクリロイル基を含む化合物であれば、単官能あるいは多官能、またはその両方の混合物であっても構わず、種々の化合物を制限なく用いることができる。 Furthermore, as a component of the fluorine-containing composition (A) having a fluorine atom content of 20% by weight or more, a non-fluorine polymerizable monomer (A3) or a non-fluorine polymer (A4) can also be exemplified. The non-fluorine polymerizable monomer (A3) is a monofunctional or polyfunctional, or a mixture of both, as long as it is a compound that does not contain a fluorine atom in the molecule and contains an acryloyl group and / or a methacryloyl group. Of course, various compounds can be used without limitation.
非フッ素重合性単量体（Ａ３）としては、特に、限定されないが、例えば、メチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、iso−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、iso−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イシステアリル（メタ）アクリレート等の脂肪族（メタ）アクリレート、グリセロール（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ブトキシエチレングリコール（メタ）アクリレート、Ｎ，Ｎ，−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ，−ジメチルアミノエチル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジプロピレングルコール（メタ）アクリレート、フェノキシポリプロピレングルコール（メタ）アクリレート、ＡＲ−２００、ＭＲ−２６０、ＡＲ−２００、ＡＲ−２０４、ＡＲ−２０８、ＭＲ−２００、ＭＲ−２０４、ＭＲ−２０８（以上、大八化学株式会社製）、ビスコート ２０００、ビスコート ２３０８（以上、大阪有機化学工業株式会社製）、ポリブタジエン（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール−ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール−ポリブチレングリコール（メタ）アクリレート、ポリスチリルエチル（メタ）アクリレート、ライトエステル ＨＯＡ−ＭＳ、ライトエステルＨＯＭＳ（以上、共栄社化学株式会社製）ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（メタ）アクリレート、フェニル（メタ）アクリレート、ネオマー ＮＡ−３０５、ネオマー ＢＡ−６０１、ネオマー ＴＡ−５０５、ネオマー ＴＡ−４０１、ネオマー ＰＨＡ−４０５Ｘ、ネオマー ＴＡ７０５Ｘ、ネオマー ＥＡ４００Ｘ、ネオマー ＥＥ４０１Ｘ、ネオマー ＥＰ４０５Ｘ、ネオマー ＨＢ６０１Ｘ、ネオマー ＨＢ６０５Ｘ（以上、三洋化成工業株式会社製）、ＫＡＹＡＲＡＤ ＨＹ−２２０、ＫＡＹＡＲＡＤ ＨＸ−６２０、ＫＡＹＡＲＡＤ Ｄ−３１０、ＫＡＹＡＲＡＤ Ｄ−３２０、ＫＡＹＡＲＡＤ Ｄ−３３０、ＫＡＹＡＲＡＤ ＤＰＨＡ、ＫＡＹＡＲＡＤ ＤＰＣＡ−２０、ＫＡＹＡＲＡＤ ＤＰＣＡ−３０、ＫＡＹＡＲＡＤ ＤＰＣＡ−６０、ＫＡＹＡＲＡＤ ＤＰＣＡ−１２０（以上、日本化薬株式会社製）等も挙げられる。これらの中でも、硬度等の力学物性を考慮すると、非含フッ素重合性単量体（Ａ３）としては、その一部又は全部に２官能以上の反応性基を有することが好ましい。 Although it does not specifically limit as a non-fluorine polymerizable monomer (A3), For example, methyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate , Iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl Aliphatic (meth) acrylates such as (meth) acrylate, istearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl ( Meta Acrylate, allyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, N, N, -diethylaminoethyl (meth) acrylate, N, N, -dimethylaminoethyl (meth) acrylate, 2- Methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxypolypro Renglecol (meth) acrylate, AR-200, MR-260, AR-200, AR-204, AR-208, MR-200, MR-204, MR-208 (above, manufactured by Daihachi Chemical Co., Ltd.), Biscote 2000 , Biscoat 2308 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), polybutadiene (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene Glycol (meth) acrylate, polystyrylethyl (meth) acrylate, light ester HOA-MS, light ester HOMS (above, manufactured by Kyoeisha Chemical Co., Ltd.) benzyl (meth) acrelan , Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate , Phenyl (meth) acrylate, neomer NA-305, neomer BA-601, neomer TA-505, neomer TA-401, neomer PHA-405X, neomer TA705X, neomer EA400X, neomer EE401X, neomer EP405X, neomer HB601X, neomer HB605X ( Sanyo Chemical Industries, Ltd.), KAYARAD HY-220, KAYARAD HX-620, KAYARAD D-310, K AYARAD D-320, KAYARAD D-330, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.) and the like are also included. Among these, in consideration of mechanical properties such as hardness, the non-fluorinated polymerizable monomer (A3) preferably has a bifunctional or higher functional group in part or all thereof.
非フッ素重合体（Ａ４）は、該組成物を目的とする塗布、成形作業性に合致した粘度に調整し、あるいは硬化物に使用目的に適した力学特性を付与する場合に導入する成分である。非フッ素重合体（Ａ４）は重合体中にフッ素原子を含有しないものであればよく、非フッ素重合体（Ａ４）は、反応性基を含有するものであっても、あるいは反応性基を含有していないものであっても構わない。 The non-fluorine polymer (A4) is a component to be introduced when the viscosity of the composition is adjusted to match the intended application and molding workability, or when the cured product is given mechanical properties suitable for the intended use. . The non-fluorine polymer (A4) only needs to contain no fluorine atom in the polymer, and the non-fluorine polymer (A4) may contain a reactive group or a reactive group. It does not matter if it is not.
次に、含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオール（Ｂ）について述べる。含フッ素多官能チオール（Ｂ）は硬化物中に柔軟な架橋部位を付与し、硬化物のガラス基材への接着性を向上させる成分である。特に、含フッ素多官能チオール（Ｂ）は、一般的に入手可能な非フッ素多官能チオールを用いると実現が困難である、フッ素原子含有量が２０重量％以上である含フッ素組成物（Ａ）に対する良好な相溶性を示し、透明な硬化物を与える成分である。含フッ素多官能チオール（Ｂ）は含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオールであれば、特に制限なく用いることが出来る。なお、本願発明において、含フッ素基とは、フッ素原子が結合した官能基を意味する。 Next, the fluorine-containing polyfunctional thiol (B) containing a fluorine-containing group and two or more mercapto groups in one molecule will be described. The fluorine-containing polyfunctional thiol (B) is a component that imparts a flexible crosslinking site in the cured product and improves the adhesion of the cured product to the glass substrate. In particular, the fluorine-containing polyfunctional thiol (B) is difficult to be realized by using a generally available non-fluorine polyfunctional thiol, and the fluorine-containing composition (A) having a fluorine atom content of 20% by weight or more. It is a component that exhibits a good compatibility with respect to and gives a transparent cured product. The fluorine-containing polyfunctional thiol (B) can be used without particular limitation as long as it is a fluorine-containing polyfunctional thiol containing a fluorine-containing group and two or more mercapto groups in one molecule. In the present invention, the fluorine-containing group means a functional group to which a fluorine atom is bonded.
含フッ素多官能チオール（Ｂ）は、含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオールであれば、特に制限なく用いることが出来る。前記含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオール類の中でも、更に、少なくとも、１個のスルフィド構造を有する化合物が好ましい。これらの化合物の中でも、原料入手の容易さ、あるいは合成の容易さから、含フッ素α，β−不飽和カルボニル化合物（Ｘ）と、１分子中に３個以上のメルカプト基とを有する化合物（Ｙ）とを反応して得られる化合物が好ましい。 The fluorine-containing polyfunctional thiol (B) can be used without particular limitation as long as it is a fluorine-containing polyfunctional thiol containing a fluorine-containing group and two or more mercapto groups in one molecule. Of the fluorine-containing polyfunctional thiols containing the fluorine-containing group and two or more mercapto groups in one molecule, a compound having at least one sulfide structure is preferred. Among these compounds, a compound containing a fluorine-containing α, β-unsaturated carbonyl compound (X) and three or more mercapto groups in one molecule (Y ) Is preferred.
また、原料の入手においての面から、特に好ましくは前記含フッ素α，β−不飽和カルボニル化合物（Ｘ）として、下記一般式（Ｉ）で表される化合物を用いる場合である（式中、Ｒｆは炭素数１〜２０の直鎖状のフロロアルキル基、炭素数１〜２０の分岐状フロロアルキル基、又は主鎖中に酸素原子が介入した炭素数１〜２０のパ−フロロアルキル基、又は部分フッ素化アルキル基を表わし、Ｘは２価の連結基を表わし、Ｒは、水素原子またはメチル基を表わす。 Further, from the viewpoint of obtaining raw materials, it is particularly preferable to use a compound represented by the following general formula (I) as the fluorine-containing α, β-unsaturated carbonyl compound (X) (wherein Rf Is a linear fluoroalkyl group having 1 to 20 carbon atoms, a branched fluoroalkyl group having 1 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 20 carbon atoms in which an oxygen atom intervenes in the main chain, or Represents a partially fluorinated alkyl group, X represents a divalent linking group, and R represents a hydrogen atom or a methyl group.
前記一般式（Ｉ）中の２価の連結基Ｘとしては、例えば、−（ＣＨ２）ｎ−、−ＣＨ２ＣＨ（ＯＨ）（ＣＨ２）ｎ−、−（ＣＨ２）ｎＮ（Ｒ２）ＳＯ２−、−（ＣＨ２）ｎＮ（Ｒ２）ＣＯ−（式中、ｎは１〜１０の整数であり、Ｒ２は水素原子又は炭素数１〜１８のアルキル基である。）、−ＣＨ（ＣＨ３）−、−ＣＨ（ＣＨ２ＣＨ３）−、−Ｃ（ＣＨ３）２−等の連結基が挙げられ、前記一般式（１）中のＲｆとしては、例えば、−Ｃ４Ｆ９、−Ｃ６Ｆ１３、−Ｃ７Ｆ１５、−Ｃ８Ｆ１７、−（ＣＦ２）４Ｈ、−（ＣＦ２）６ＣＦ（ＣＦ３）２、−（ＯＣＦ２ＣＦ２）４ＯＣＦ２ＣＦ３、−（ＯＣＦ２ＣＦ（ＣＦ３））３Ｃ３Ｆ７等のフッ素化アルキル基が挙げられる。 Examples of the divalent linking group X in the general formula (I) include — (CH 2 ) n —, —CH 2 CH (OH) (CH 2 ) n —, and — (CH 2 ) n N (R 2) SO 2 -, - ( CH 2) n n (R 2) CO- ( wherein, n is an integer from 1 to 10, R 2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ), —CH (CH 3 ) —, —CH (CH 2 CH 3 ) —, —C (CH 3 ) 2 — and the like. Examples of Rf in the general formula (1) include: -C 4 F 9, -C 6 F 13, -C 7 F 15, -C 8 F 17, - (CF 2) 4 H, - (CF 2) 6 CF (CF 3) 2, - (OCF 2 CF 2) 4 OCF 2 CF 3, - (OCF 2 CF (CF 3)) and a fluorinated alkyl group such as 3 C 3 F 7.
前記フッ素化（メタ）アクリレート（Ｘ）の好ましいものとしては、例えば、以下の化合物が挙げられる。
Ｘ−１ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ８Ｆ１７
Ｘ−２ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ８Ｆ１７
Ｘ−３ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ１２Ｆ２５
Ｘ−４ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ１２Ｆ２５
Ｘ−５ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ６Ｆ１３
Ｘ−６ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ６Ｆ１３
Ｘ−７ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｃ４Ｆ９
Ｘ−８ ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＨ２Ｃ４Ｆ９
Ｘ−９ ：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＦ３
Ｘ−１０：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＦ（ＣＦ３）２
Ｘ−１１：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣＨ２ＣＦＨＣＦ３
Ｘ−１２：ＣＨ２＝ＣＨＣＯＯＣＨ２（ＣＦ２）６Ｈ
Ｘ−１３：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｃ８Ｆ１７
Ｘ−１４：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｎ（Ｃ３Ｈ７）ＳＯ２Ｃ８Ｆ１７
Ｘ−１５：ＣＨ２＝ＣＨＣＯＯＣＨ２ＣＨ２Ｎ（Ｃ２Ｈ５）ＣＯＣ７Ｆ１５
Ｘ−１６：ＣＨ２＝ＣＨＣＯＯＣ２Ｈ４（ＣＦ（ＣＦ３）ＯＣＦ２）３Ｃ２Ｆ５
Ｘ−１７：ＣＨ２＝ＣＨＣＯＯＣＨ２（ＣＦ（ＣＦ３）ＯＣＦ２）２Ｃ２Ｆ５
以上、含フッ素α，β−不飽和カルボニル化合物（Ｘ）を例示したが、これらによって本特許が何ら制限されるものではない。
Preferable examples of the fluorinated (meth) acrylate (X) include the following compounds.
X-1: CH 2 = CHCOOCH 2 CH 2 C 8 F 17
X-2: CH 2 = C (CH 3) COOCH 2 CH 2 C 8 F 17
X-3: CH 2 = CHCOOCH2CH 2 C 12 F 25
X-4: CH 2 = C (CH 3) COOCH 2 CH 2 C 12 F 25
X-5: CH 2 = CHCOOCH 2 CH 2 C 6 F 13
X-6: CH 2 = C (CH 3) COOCH 2 CH 2 C 6 F 13
X-7: CH 2 = CHCOOCH 2 CH 2 C4F9
X-8: CH 2 = C (CH 3) COOCH 2 CH 2 C 4 F 9
X-9: CH 2 = CHCOOCH 2
X-10: CH 2 = C (CH 3) COOCH 2 CF (CF 3) 2
X-11: CH 2 = C (CH 3) COOCH 2
X-12: CH 2 = CHCOOCH 2 (CF 2) 6 H
X-13: CH 2 = CHCOOCH 2 CH (OH) CH 2 C 8 F 17
X-14: CH 2 = CHCOOCH 2 CH 2 N (C 3 H 7) SO 2 C 8 F 17
X-15: CH 2 = CHCOOCH 2 CH 2 N (C 2 H 5) COC 7 F 15
X-16: CH 2 = CHCOOC 2 H 4 (CF (CF 3) OCF 2) 3 C 2
X-17: CH 2 = CHCOOCH 2 (CF (CF 3) OCF 2) 2 C 2
The fluorine-containing α, β-unsaturated carbonyl compound (X) has been exemplified above, but the present patent is not limited by these.
前記の化合物を用いて合成した含フッ素多官能チオール（Ｂ）として前記化合物（Ｘ−１）と、後述する１分子中に３個以上のメルカプト基を有する化合物（Ｙ）としてペンタエリスリトールテトラキスチオプロピオネートを反応して得られる化合物を例にとれば、下記構造式（Ｂ−１）が挙げられる。 The compound (X-1) as the fluorine-containing polyfunctional thiol (B) synthesized using the compound, and pentaerythritol tetrakisthiopro as the compound (Y) having three or more mercapto groups in one molecule described later. Taking the compound obtained by reacting pionate as an example, the following structural formula (B-1) may be mentioned.
前記式中のｍは、１または２の整数を表わす。 M in the above formula represents an integer of 1 or 2.
前記含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオール（Ｂ）は、硬化物中に柔軟な架橋部位を付与し、硬化物のガラス基材への接着性を向上させる成分であり、含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオールであれば、特に制限なく用いることが出来るが、原料入手の容易さ、あるいは合成の容易さから、含フッ素α，β−不飽和カルボニル化合物（Ｘ）と１分子中に３個以上のメルカプト基を有する化合物（Ｙ）とを反応して得られる化合物が好ましく、原料の入手の容易さから、特に好ましくは前記の１分子中に３個以上のメルカプト基を有する化合物（Ｙ）として、下記一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）からなる群から選ばれる少なくとも一種の化合物を用いる場合である。 The fluorine-containing polyfunctional thiol (B) containing the fluorine-containing group and two or more mercapto groups in one molecule gives a flexible cross-linking site in the cured product, and the adhesion of the cured product to the glass substrate. As long as it is a fluorine-containing polyfunctional thiol containing a fluorine-containing group and two or more mercapto groups in one molecule, it can be used without particular limitation. From the viewpoint of ease, a compound obtained by reacting a fluorine-containing α, β-unsaturated carbonyl compound (X) with a compound (Y) having three or more mercapto groups in one molecule is preferable. In view of easiness, at least one selected from the group consisting of the following general formulas (II), (III) and (IV) is particularly preferable as the compound (Y) having three or more mercapto groups in one molecule. Use compound This is the case.
（式中、ｍ及びｎは、それぞれ独立に１〜８の整数を表わし、Ｒ２は一般式（Ｖ）又は（ＶＩ）から選択される。また、Ｒ３、Ｒ４及びＲ５は各々独立に一般式（ＶＩＩ）又は（ＶＩＩＩ）から選択される。一般式（Ｖ）〜（ＶＩＩＩ）中で、ｘは１〜８の整数を表わし、ｙは０〜６の整数を表わし、ｚはｚ≦６−ｙを満たす正の整数を表わす。Ｒ３、Ｒ４及びＲ５は各々独立に、−Ｒ６ＯＣＯＲ７ＳＨを表し、Ｒ６及びＲ７は各々独立に、炭素数１〜８のアルキレン基を表わす。） (In the formula, m and n each independently represent an integer of 1 to 8, R 2 is selected from the general formula (V) or (VI). Also, R 3 , R 4 and R 5 are each independently selected. In the general formulas (V) to (VIII), x represents an integer of 1 to 8, y represents an integer of 0 to 6, and z represents z. Represents a positive integer satisfying ≦ 6-y, R 3 , R 4 and R 5 each independently represent —R 6 OCOR 7 SH, and R 6 and R 7 each independently represent a group having 1 to 8 carbon atoms. Represents an alkylene group.)
１分子中に３個以上のメルカプト基を有する化合物（Ｙ）としては、入手の容易さから、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、ペンタエリスリトールテトラキスチオプロピオネート、トリメチロールプロパントリス（３−メルカプトブチレート）、ペンタエリスリトールテトラキス（３−メルカプトブチレート）、トリス（メルカプトグリコロキシエチル）イソシアヌレート、トリス（メルカプトプロピオノキシエチル）イソシアヌレート、トリス（３−メルカプトブチロノキシエチル）イソシアヌレートからなる群から選ばれる少なくとも一種の化合物を用いることが特に好ましい。 As the compound (Y) having three or more mercapto groups in one molecule, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhiopropionate, penta Erythritol tetrakisthiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (mercaptoglycoxyethyl) isocyanurate, tris (mercaptopropionoxyethyl) isocyanurate It is particularly preferable to use at least one compound selected from the group consisting of tris (3-mercaptobutyronoxyethyl) isocyanurate.
前記化合物（Ｘ）と前記化合物（Ｙ）との反応比率としては、前記化合物（Ｘ）と前記化合物（Ｙ）との反応で得られる反応生成物が、１分子中に２個以上のメルカプト基を有するように調整する。また、前記化合物（Ｘ）と前記化合物（Ｙ）との反応条件としては、通常の求核付加反応の方法に従えば良く、フッ素原子を有することによる特別の配慮は特に必要ではなく、無溶媒でも溶媒存在下でも製造できる。溶媒を使用する場合には、前記化合物（Ｘ）及び前記化合物（Ｙ）の溶解性、沸点、使用する設備等を考慮し適宜、選択されるものであるが、具体的には、酢酸エチル、酢酸ブチル等のエステル類、ジクロロメタン、１，２−ジクロロエタン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族系炭化水素類、アセトン、メチルエチルケトン（以下、ＭＥＫと略記する。）、メチルイソブチルケトン（以下、ＭＩＢＫと略記する。）等のケトン類、メタノール、エタノール、２−プロパノール等のアルコール類、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の非プロトン性極性化合物、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ヘキサン、ヘプタン等の脂肪族系炭化水素類等が挙げられ、単独でも２種以上の溶媒を混合して使用しても良い。これらの中でもエステル類、芳香族系炭化水素類、ケトン類、アルコール類、エーテル類、ジメチルホルムアミド、ジメチルスルホキシド等を用いることが好ましく、エステル類、ケトン類、アルコール類、エーテル類を用いることが特に好ましい。 The reaction ratio between the compound (X) and the compound (Y) is that the reaction product obtained by the reaction between the compound (X) and the compound (Y) has two or more mercapto groups in one molecule. Adjust to have In addition, the reaction condition between the compound (X) and the compound (Y) may be the usual nucleophilic addition reaction method, and special considerations due to having a fluorine atom are not particularly required. However, it can also be produced in the presence of a solvent. When a solvent is used, it is appropriately selected in consideration of the solubility, boiling point, equipment used, etc. of the compound (X) and the compound (Y). Specifically, ethyl acetate, Esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl isobutyl ketone (Hereinafter abbreviated as MIBK), alcohols such as methanol, ethanol and 2-propanol, aprotic polar compounds such as dimethylformamide, dimethylacetamide and dimethylsulfoxide, and ethers such as diethyl ether and tetrahydrofuran Aliphatic hydrocarbons such as hexane, heptane, etc. But it may be used by mixing two or more solvents. Among these, it is preferable to use esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformamide, dimethyl sulfoxide, etc., and it is particularly preferable to use esters, ketones, alcohols, ethers. preferable.
この反応は、無触媒で行うことも可能であるが、反応効率の面から、適宜、触媒等の反応助剤を選択して使用することも可能である。前記反応助剤として、例えば、ナトリウムメトキシド、ナトリウムエトキシド等の金属アルコラート類、トリメチルアミン、トリエチルアミン、１，４−ジアザビシクロ−［２，２，２］−オクタン等のアミン類、水素化ナトリウム、水素化リチウム等の金属水素化物類、ベンジルトリメチルアンモニウム・ヒドロキシド、テトラアンモニウム・フルオライド等のアンモニウム塩、過酢酸等の過酸化物等が挙げられ、好ましくは金属アルコラート類、アミン類、アンモニウム塩であり、特に好ましくはアミン類である。前記反応助剤の使用量としては、特に制限されるものではないが、原料として用いる前記化合物（Ｘ）１モルに対して０．０１〜５０モル％、好ましくは０．１〜２０モル％である。 This reaction can be performed without a catalyst, but from the viewpoint of reaction efficiency, a reaction aid such as a catalyst can be appropriately selected and used. Examples of the reaction assistant include metal alcoholates such as sodium methoxide and sodium ethoxide, amines such as trimethylamine, triethylamine and 1,4-diazabicyclo- [2,2,2] -octane, sodium hydride, hydrogen Metal hydrides such as lithium iodide, ammonium salts such as benzyltrimethylammonium hydroxide, tetraammonium fluoride, peroxides such as peracetic acid, etc., preferably metal alcoholates, amines, ammonium salts Particularly preferred are amines. The amount of the reaction aid used is not particularly limited, but is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on 1 mol of the compound (X) used as a raw material. is there.
さらに、用いる化合物（Ｘ）及び化合物（Ｙ）によっては、熱も反応活性化エネルギー源として単独使用または併用使用することが可能である。反応温度としては通常、０℃〜還流温度であり、好ましくは２０〜１００℃、特に好ましくは２０〜７０℃である。反応時、溶媒などを使用した場合、溶質濃度としては通常２〜９０重量％であり、好ましくは２０〜８０重量％である。反応資材の投入順序としては特に制限されない。このようにして得られた生成物は、抽出などによる洗浄、およびカラムクロマトグラフィー等で精製して使用することも可能であるが、そのまま使用することも可能である。 Furthermore, depending on the compound (X) and compound (Y) used, heat can be used alone or in combination as a reaction activation energy source. The reaction temperature is usually 0 ° C. to reflux temperature, preferably 20 to 100 ° C., particularly preferably 20 to 70 ° C. When a solvent or the like is used during the reaction, the solute concentration is usually 2 to 90% by weight, preferably 20 to 80% by weight. There is no particular limitation on the order of the reaction materials. The product thus obtained can be used after being purified by extraction, column chromatography, or the like, but can also be used as it is.
前記、含フッ素基と１分子中に少なくとも２個以上のメルカプト基を含有する含フッ素多官能チオール（Ｂ）は、硬化物のガラス基材への密着性を十分に発揮させ、かつ組成物の硬化性、硬化物の力学物性を考慮すると、フッ素原子含有量が２０％以上の含フッ素組成物（Ａ）１００重量に対し、０．０１〜２０重量部の範囲で含むことが好ましく、強固な密着性を発現するためには０．０５〜１０重量部の範囲で含むことがより好ましく、特に好ましくは０．２〜１０重量部の範囲である。 The fluorine-containing polyfunctional thiol (B) containing the fluorine-containing group and at least two or more mercapto groups in one molecule sufficiently exhibits the adhesiveness of the cured product to the glass substrate, and In view of curability and mechanical properties of the cured product, it is preferable that the content is 0.01 to 20 parts by weight with respect to 100 parts by weight of the fluorine-containing composition (A) having a fluorine atom content of 20% or more. In order to express adhesiveness, it is more preferable to contain in 0.05-10 weight part, Especially preferably, it is 0.2-10 weight part.
本発明の含フッ素組成物は、フッ素原子含有量が２０重量％以上である含フッ素組成物（Ａ）中に、含フッ素基と１分子中に２個以上のメルカプト基を含有する含フッ素多官能チオール（Ｂ）を含むこと以外に何ら制限されるものではなく、目的に応じて各種溶剤、アクリル樹脂、ＰＴＦＥ（ポリテトラフルオロエチレン）、ポリエチレン、カーボン、酸化チタン、アルミナ、銅、シリカ微粒子等の有機又は無機粒子、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、酸化防止剤、防錆剤、スリップ剤、ワックス、艶調整剤、離型剤、相溶化剤、導電調整剤、顔料、染料、分散剤、分散安定剤、シリコーン系、フッ素系または炭化水素系界面活性剤等の公知の各種添加剤を併用することが可能である。 The fluorine-containing composition of the present invention is a fluorine-containing composition containing a fluorine-containing group and two or more mercapto groups in one molecule in the fluorine-containing composition (A) having a fluorine atom content of 20% by weight or more. It is not limited in any way other than containing the functional thiol (B), and various solvents, acrylic resins, PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, alumina, copper, silica fine particles, etc. depending on the purpose Organic or inorganic particles, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss regulators, mold release agents Various known additives such as compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, silicone-based, fluorine-based or hydrocarbon-based surfactants can be used in combination.
本発明で得られる含フッ素組成物は、塗布や成形加工後そのまま用いても、加工後硬化処理を行っても良い。硬化処理を行う場合、その硬化条件に制限はなく、熱、紫外線、電子線等のエネルギー線硬化、又はそれらを併用する硬化方法を、目的に応じて選択可能であるが、装置の汎用性および生産性の点からは紫外線硬化が好ましい。紫外線硬化を行う場合に用いる光開始剤としては、種々のものを使用することができ、特に制限はなく、例えば、ベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾインエチルエーテル、ベンゾインイソブチルエーテル、ベンジルメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチルー１−フェニル−１−オン、１−（４’−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、１−（４’−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン等を挙げることができる。また、硬化条件、製造設備によっては種々の増感剤を併用することも可能である。 The fluorine-containing composition obtained in the present invention may be used as it is after coating or molding, or may be subjected to a post-processing curing treatment. When performing the curing treatment, the curing conditions are not limited, and energy ray curing such as heat, ultraviolet rays, and electron beams, or a curing method using them together can be selected according to the purpose. From the viewpoint of productivity, ultraviolet curing is preferable. As the photoinitiator used for UV curing, various types can be used, and there is no particular limitation. For example, benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, 1- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1- (4′-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4′-dodecyl) And phenyl) -2-hydroxy-2-methylpropan-1-one. Various sensitizers can be used in combination depending on the curing conditions and production equipment.
また、含フッ素組成物は、塗布や成形等の加工工程において、組成、基材の種類、用途、目的等に応じて、乾燥、エージング操作を行うことも可能である。
In addition, the fluorine-containing composition can be subjected to drying and aging operations in processing steps such as coating and molding depending on the composition, the type of base material, application, purpose, and the like.
本発明の含フッ素組成物を適用する基材にも制限はなく、例えばガラス、ＰＥＴ、ポリカーボネート樹脂（ＰＣ）、メタクリル樹脂（ＰＭＭＡ）、不飽和ポリエステル樹脂等のプラスチック、アルミ、銅等の金属等を用いることが可能であるが、特にガラスに対する効果は顕著である。ガラス基材を用いる場合、ガラス基材の形状、サイズ、厚み等を問わず使用することが可能である。ガラス基材は、そのまま用いても、より接着性を向上させるためにシランカップリング処理を施したものであっても、接着性や帯電防止性等の改良を目的にプラズマ処理やコロナ処理を行ったものでも構わない。 There is no restriction | limiting also in the base material to which the fluorine-containing composition of this invention is applied, For example, metals, such as glass, PET, polycarbonate resin (PC), methacryl resin (PMMA), unsaturated polyester resin, aluminum, copper, etc. However, the effect on glass is particularly remarkable. When using a glass substrate, it can be used regardless of the shape, size, thickness, etc. of the glass substrate. Even if the glass substrate is used as it is or has been subjected to silane coupling treatment to improve adhesion, plasma treatment or corona treatment is performed for the purpose of improving adhesion and antistatic properties. It does n’t matter.
また、含フッ素組成物のコーティング方法や硬化、乾燥、エージング条件にも制限はない。コーターは、用途と目的に応じて選択され、グラビアコーター、ナイフコーター、デイッピング塗布、スプレー塗布、スピンコーター、スリット＆スピンコーター、スリットコーター、ロールコーター、カーテンコーター、フローコーター、刷毛塗り等の方法により各種基材上に塗布することができる。 Moreover, there is no restriction | limiting also in the coating method, hardening, drying, and aging conditions of a fluorine-containing composition. The coater is selected according to the application and purpose, and it depends on the gravure coater, knife coater, dipping coating, spray coating, spin coater, slit & spin coater, slit coater, roll coater, curtain coater, flow coater, brush coating, etc. It can apply | coat on various base materials.
本発明の含フッ素組成物の用途にも特に制限はなく、例えば、各種基材に対する接着剤、ハードコーティング剤、反射防止膜材等における低屈折率性、低反射性と接着性を両立する光学コーティング用途、低誘電率性を利用した絶縁膜等が挙げられ、建材、自動車、フィルム、ＯＡ機器、電気・電子機器、フラットパネルディスプレイ、半導体、通信機器等の分野に応用できる。具体的な用途例としては、自動車窓材、屋根材、高速道路用保護板、カーポート、プロジェクションテレビ、携帯電話、デジタルカメラ、ビデオカメラ等の前面板、各種タッチパネル、液晶ディスプレイの偏光板、ＣＲＴディスプレイ、プラズマディスプレイ、眼鏡レンズ、レンズシート、各種光学部品、半導体、液晶基板用層間絶縁膜、電気・電子機器のハウジング等に対するコーティング用途等が挙げられる。 The use of the fluorine-containing composition of the present invention is not particularly limited. For example, an optical material that achieves both low refractive index, low reflectivity, and adhesiveness in adhesives, hard coating agents, antireflection film materials and the like for various substrates. Examples include coating applications, insulating films using low dielectric constants, and the like, and can be applied to fields such as building materials, automobiles, films, OA equipment, electrical / electronic equipment, flat panel displays, semiconductors, and communication equipment. Specific examples of applications include automobile window materials, roofing materials, protective plates for highways, carports, projection TVs, mobile phones, digital cameras, video cameras, front panels, various touch panels, liquid crystal display polarizing plates, CRTs, etc. Examples include displays, plasma displays, spectacle lenses, lens sheets, various optical components, semiconductors, interlayer insulating films for liquid crystal substrates, and coatings for housings of electrical and electronic devices.
次に、本発明の具体的な実施例について説明するが、これらの説明によって本発明が何ら限定されるものでないことは勿論である。 Next, specific examples of the present invention will be described, but it is needless to say that the present invention is not limited to these examples.
なお、ＧＰＣの測定は東ソー(株)社製ＨＬＣ８２２０システムを用い以下の条件で行った。
分離カラム：東ソー（株）製ＴＳＫｇｅｌＳｕｐｅｒＨ−ＲＣを２本、東ソー（株）製ＴＳＫｇｅｌＧＭＨＨＲ−Ｎを４本使用。
カラム温度：４０℃
移動層：和光純薬工業（株）製テトラヒドロフラン
流速：１．０ｍｌ／分
試料濃度：０．１重量％
試料注入量：１００マイクロリットル
検出器：ELSD（蒸発光散乱検出器）
GPC was measured using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation columns: 2 TSKgelSuperH-RC manufactured by Tosoh Corporation and 4 TSKgelGMH HR- N manufactured by Tosoh Corporation.
Column temperature: 40 ° C
Moving layer: Wako Pure Chemical Industries, Ltd. Tetrahydrofuran Flow rate: 1.0 ml / min Sample concentration: 0.1% by weight
Sample injection volume: 100 microliters Detector: ELSD (evaporative light scattering detector)
実施例１ 含フッ素多官能チオール（１）の合成
温度計、冷却管、窒素ガス導入管、攪拌機を取り付けたフラスコに、ペンタエリスリトールテトラキスチオプロピオネート４８９ｇ、パーフルオロオクチルエチルアクリレート２５９ｇ、アセトン２５０ｇを投入し攪拌下、６０℃まで昇温した。その後、トリエチルアミン１０ｍＬをフラスコ内へ滴下し、還流条件下で３時間攪拌した。続いて、減圧下、トリエチルアミンを留去し、下記構造式で表わされる含フッ素多官能チオール（１）を得た。生成物は無色透明粘稠液体であった。含フッ素多官能チオール（１）の１Ｈ−ＮＭＲ、ＧＰＣチャートを図１、２に示す。ＧＰＣチャートのピーク（１）が本発明の含フッ素多官能チオール（１）である。
Example 1 Synthesis of fluorine-containing polyfunctional thiol (1) A flask equipped with a thermometer, a condenser tube, a nitrogen gas introduction tube, and a stirrer was charged with 489 g of pentaerythritol tetrakisthiopropionate, 259 g of perfluorooctylethyl acrylate, and 250 g of acetone. The temperature was raised to 60 ° C. with stirring. Thereafter, 10 mL of triethylamine was dropped into the flask and stirred for 3 hours under reflux conditions. Subsequently, triethylamine was distilled off under reduced pressure to obtain a fluorine-containing polyfunctional thiol (1) represented by the following structural formula. The product was a colorless transparent viscous liquid. 1H-NMR and GPC charts of the fluorine-containing polyfunctional thiol (1) are shown in FIGS. The peak (1) on the GPC chart is the fluorine-containing polyfunctional thiol (1) of the present invention.
実施例２ 含フッ素多官能チオール（２）の合成
温度計、冷却管、窒素ガス導入管、攪拌機を取り付けたフラスコに、ペンタエリスリトールテトラキスチオプロピオネート４８９ｇ、パーフルオロオクチルエチルアクリレート５１８ｇ、アセトン２５０ｇを投入し攪拌下、６０℃まで昇温した。その後、トリエチルアミン１０ｍＬをフラスコ内へ滴下し、還流条件下で３時間攪拌した。続いて、減圧下、トリエチルアミンを留去し、含フッ素多官能チオール（２）を得た。生成物は無色透明粘稠液体であった。含フッ素多官能チオール（２）の１Ｈ−ＮＭＲ、ＧＰＣチャートを図３、４に示す。
Example 2 Synthesis of fluorinated polyfunctional thiol (2) A flask equipped with a thermometer, a condenser tube, a nitrogen gas introduction tube, and a stirrer was charged with 489 g of pentaerythritol tetrakisthiopropionate, 518 g of perfluorooctylethyl acrylate, and 250 g of acetone. The temperature was raised to 60 ° C. with stirring. Thereafter, 10 mL of triethylamine was dropped into the flask and stirred for 3 hours under reflux conditions. Subsequently, triethylamine was distilled off under reduced pressure to obtain a fluorine-containing polyfunctional thiol (2). The product was a colorless transparent viscous liquid. FIGS. 3 and 4 show 1H-NMR and GPC charts of the fluorine-containing polyfunctional thiol (2).
実施例３ 含フッ素多官能チオール（３）の合成
温度計、冷却管、窒素ガス導入管、攪拌機を取り付けたフラスコに、トリス（３−メルカプトブチロノキシエチル）イソシアヌレート５２８ｇ、パーフルオロオクチルエチルアクリレート２５９ｇ、アセトン２５０ｇを投入し攪拌下、６０℃まで昇温した。その後、トリエチルアミン１０ｍＬをフラスコ内へ滴下し、還流条件下で４時間攪拌した。続いて、減圧下、トリエチルアミンを留去し、含フッ素多官能チオール（３）を７８０ｇ（収率９９重量％）得た。生成物は無色透明粘稠液体であった。含フッ素多官能チオール（３）の１Ｈ−ＮＭＲ、ＧＰＣチャートを図５、６に示す。
Example 3 Synthesis of fluorine-containing polyfunctional thiol (3) In a flask equipped with a thermometer, a condenser tube, a nitrogen gas introduction tube, and a stirrer, 528 g of tris (3-mercaptobutyronoxyethyl) isocyanurate, perfluorooctylethyl acrylate 259 g and acetone 250 g were added and heated to 60 ° C. with stirring. Thereafter, 10 mL of triethylamine was dropped into the flask and stirred for 4 hours under reflux conditions. Subsequently, triethylamine was distilled off under reduced pressure to obtain 780 g (yield 99% by weight) of fluorine-containing polyfunctional thiol (3). The product was a colorless transparent viscous liquid. 1H-NMR and GPC charts of the fluorine-containing polyfunctional thiol (3) are shown in FIGS.
実施例４
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（１）を３部添加して得られる、フッ素原子含有量が５０重量％の含フッ素組成物（１）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 4
3 parts of fluorine-containing polyfunctional thiol (1) is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. The fluorine-containing composition (1) having a fluorine atom content of 50% by weight obtained by adding a part thereof is applied to a glass substrate using a 0.152 mm applicator and irradiated with a metal halide lamp with an output of 120 W / cm. Cured at 2000 mJ / cm 2 . The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例５
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（２）を３部添加して得られる、フッ素原子含有量が５０重量％の含フッ素組成物（２）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 5
3 parts of fluorine-containing polyfunctional thiol (2) is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. The fluorine-containing composition (2) having a fluorine atom content of 50% by weight obtained by adding a part thereof is applied to a glass substrate using a 0.152 mm applicator and irradiated with a metal halide lamp with an output of 120 W / cm. Cured at 2000 mJ / cm 2 . The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例６
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（３）を３部添加して得られる、フッ素原子含有量が５０重量％の含フッ素組成物（３）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 6
3 parts of fluorine-containing polyfunctional thiol (3) is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. A fluorine-containing composition (3) having a fluorine atom content of 50% by weight obtained by adding a part thereof is applied to a glass substrate using a 0.152 mm applicator and irradiated with a metal halide lamp with an output of 120 W / cm. Cured at 2000 mJ / cm 2 . The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例７
ペンタコサフルオロテトラデシルアクリレート９０部、トリメチロールプロパントリアクリレート６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（５）を３部添加して得られる、フッ素原子含有量が６０重量％の含フッ素組成物（５）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 7
Fluorine-containing polyfunctional thiol (5) is added to 100 parts of a composition comprising 90 parts of pentacosafluorotetradecyl acrylate, 6 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. The fluorine-containing composition (5) having a fluorine atom content of 60% by weight obtained by adding 3 parts is applied to a glass substrate using a 0.152 mm applicator and irradiated with a metal halide lamp with an output of 120 W / cm. Curing was performed at an amount of 2000 mJ / cm 2 . The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例８
ノナフルオロヘキシルアクリレート４０部、ジシクロペンタニルアクリレート２０部、イソボニルアクリレート２０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（６）を３部添加して得られる、フッ素原子含有量が２２重量％の含フッ素組成物（６）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 8
100 parts of a composition comprising 40 parts nonafluorohexyl acrylate, 20 parts dicyclopentanyl acrylate, 20 parts isobonyl acrylate, 16 parts trimethylolpropane triacrylate, 4 parts 2-hydroxy-2-methyl-1-phenylpropanone On the other hand, a fluorine-containing composition (6) having a fluorine atom content of 22% by weight obtained by adding 3 parts of fluorine-containing polyfunctional thiol (6) is applied to a glass substrate using a 0.152 mm applicator. And cured with an irradiation energy amount of 2000 mJ / cm 2 with a metal halide lamp having an output of 120 W / cm. The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例９
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（１）を０．２部添加して得られる、フッ素原子含有量が５０重量％の含フッ素組成物（１１）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 9
Fluorine-containing polyfunctional thiol (1) is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. .2 parts of a fluorine-containing composition (11) having a fluorine atom content of 50% by weight is applied to a glass substrate with a 0.152 mm applicator and irradiated with a metal halide lamp with an output of 120 W / cm. It hardened | cured by energy amount 2000mJ / cm < 2 >. The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
実施例１０
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、含フッ素多官能チオール（１）を９部添加して得られる、フッ素原子含有量が５０重量％の含フッ素組成物（１２）を、ガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Example 10
9 parts of fluorine-containing polyfunctional thiol (1) is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone. The fluorine-containing composition (12) having a fluorine atom content of 50% by weight obtained by adding a part thereof is applied to a glass substrate using a 0.152 mm applicator, and the irradiation energy amount with a metal halide lamp with an output of 120 W / cm Cured at 2000 mJ / cm 2 . The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
比較例１
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物をガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価、また密着性を碁盤目密着試験により評価した。
Comparative Example 1
A composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone is applied to a glass substrate using a 0.152 mm applicator and output. It hardened | cured with the irradiation energy amount of 2000 mJ / cm < 2 > with the 120 W / cm metal halide lamp. The curability was evaluated by a tactile sensation by touch, the appearance of the coating film was visually evaluated, and the adhesion was evaluated by a cross-cut adhesion test.
比較例２
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、１−ドデシルメルカプタンを３部添加した組成物１をガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価したところ硬化性が不十分であったため、密着性の評価は行なわなかった。塗膜の外観を目視で評価した。
Comparative Example 2
Composition in which 3 parts of 1-dodecyl mercaptan is added to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-
比較例３
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、トリメチロールプロパントリスチオプロピオネート３部を添加した組成物１をガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価、塗膜の外観を目視で評価したところ、塗膜が白濁していた。よって、密着性の評価は行なわなかった。
Comparative Example 3
3 parts of trimethylolpropane tristhiopropionate with respect to 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone The
比較例４
ヘプタデカフルオロデシルアクリレート８０部、トリメチロールプロパントリアクリレート１６部、２−ヒドロキシ−２−メチル−１−フェニルプロパノン４部からなる組成物１００部に対し、ヘプタデカフルオロデシルメルカプタン３部を添加した組成物１をガラス基材へ０．１５２ｍｍアプリケーターを用いて塗布、出力１２０Ｗ／ｃｍのメタルハライドランプにて照射エネルギー量２０００ｍＪ／ｃｍ２にて硬化した。硬化性を指触によるタック感で評価したところ硬化性が不十分であったため、密着性の評価は行なわなかった。塗膜の外観を目視で評価した。
Comparative Example 4
To 100 parts of a composition comprising 80 parts of heptadecafluorodecyl acrylate, 16 parts of trimethylolpropane triacrylate, and 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone, 3 parts of heptadecafluorodecyl mercaptan was added.
表１及び２において、硬化性は紫外線照射後の塗膜を指触によるタック感によって評価した。塗膜にタック感がなく、指触後も未硬化組成物が指に付着しないものを○で示し、硬化が不十分であり、指触後に未硬化組成物が指に付着するものを×で示した。塗膜外観は、ガラス基板上の塗膜を透明性を目視により、濁りが全く見られないものを◎、塗膜の外縁部に僅かに濁りを生じたものを○、塗膜全体が激しく濁ったものを×と評価した。密着性はセロハンテープによる１ｍｍ碁盤目剥離試験により評価し、剥離試験後の残存マス目が９０／１００〜１００／１００のものを◎、６０／１００〜９０／１００のものを○、３０／１００〜６０／１００のものを△、０／１００〜３０／１００のものを×、と評価した。 In Tables 1 and 2, the curability was evaluated by the tactile sensation by finger touch of the coating film after ultraviolet irradiation. The coating film has no tackiness and the uncured composition does not adhere to the finger even after touching with a circle, the curing is insufficient, and the uncured composition adheres to the finger after touching with × Indicated. As for the appearance of the coating film, the coating film on the glass substrate is visually transparent to show no turbidity ◎, the coating film slightly turbid on the outer edge ○, the entire coating film becomes turbidly turbid Was evaluated as x. Adhesion was evaluated by a 1 mm grid peel test using a cellophane tape. The remaining squares after the peel test were 90/100 to 100/100, ◎, 60/100 to 90/100, ○, 30/100. The one of ~ 60/100 was evaluated as Δ, and the one of 0/100 to 30/100 was evaluated as ×.
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| JP5550818B2 (en) * | 2008-05-09 | 2014-07-16 | 電気化学工業株式会社 | Adhesive for optical components |
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| CN105980444B (en) * | 2014-09-01 | 2017-12-15 | 日油株式会社 | Hardening resin composition |
| JPWO2016117385A1 (en) * | 2015-01-20 | 2017-10-26 | 日油株式会社 | Curable resin composition |
| JP6582774B2 (en) * | 2015-09-10 | 2019-10-02 | 日油株式会社 | Curable resin composition for release sheet, process substrate using the same, and method for protecting substrate |
| JP6569410B2 (en) * | 2015-09-10 | 2019-09-04 | 日油株式会社 | Curable resin composition for release sheet, process substrate using the same, and method for protecting substrate |
| JP6569409B2 (en) * | 2015-09-10 | 2019-09-04 | 日油株式会社 | Curable resin composition for release sheet, process substrate using the same, and method for protecting substrate |
| JP7162523B2 (en) * | 2018-12-25 | 2022-10-28 | Ａｇｃセイミケミカル株式会社 | THERMOPLASTIC RESIN COMPOSITION, MOLDED PRODUCT, AND METHOD FOR MAKING MOLDED PRODUCT |
| CN115698189A (en) * | 2020-06-30 | 2023-02-03 | Agc清美化学股份有限公司 | Thermoplastic resin composition, molded article, and method for producing molded article |
| CN115702175A (en) * | 2020-06-30 | 2023-02-14 | Agc清美化学股份有限公司 | Fluorocopolymer, thermoplastic resin composition, molded article, and process for producing molded article |
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| JPS58208344A (en) * | 1982-05-31 | 1983-12-05 | Mitsubishi Rayon Co Ltd | Heat-resistant fluororesin composition |
| JPS6365092A (en) * | 1986-09-05 | 1988-03-23 | Asahi Glass Co Ltd | Corrosion inhibitor for metal |
| JP2571584B2 (en) * | 1986-12-05 | 1997-01-16 | エヌティエヌ株式会社 | Lubricating resin composition |
| JP2003192708A (en) * | 2001-12-25 | 2003-07-09 | Fuji Photo Film Co Ltd | Polymerizable composition for optical member, optical member made therewith and method for producing the same |
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