WO2022203064A1 - (メタ)アクリル酸エステル系共重合体及び硬化性組成物 - Google Patents
(メタ)アクリル酸エステル系共重合体及び硬化性組成物 Download PDFInfo
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- WO2022203064A1 WO2022203064A1 PCT/JP2022/014602 JP2022014602W WO2022203064A1 WO 2022203064 A1 WO2022203064 A1 WO 2022203064A1 JP 2022014602 W JP2022014602 W JP 2022014602W WO 2022203064 A1 WO2022203064 A1 WO 2022203064A1
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- acid ester
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- 125000004434 sulfur atom Chemical group 0.000 claims description 25
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QRFPECUQGPJPMV-UHFFFAOYSA-N isocyanatomethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CN=C=O QRFPECUQGPJPMV-UHFFFAOYSA-N 0.000 description 1
- HENJUOQEQGBPSV-UHFFFAOYSA-N isocyanatomethyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CN=C=O HENJUOQEQGBPSV-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- ICCDZMWNLNRHGP-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-bis(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)CCCOCC1CO1 ICCDZMWNLNRHGP-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- CSNJSTXFSLBBPX-UHFFFAOYSA-N n'-(trimethoxysilylmethyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CNCCN CSNJSTXFSLBBPX-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DWYWQJWQNQLGLB-UHFFFAOYSA-N n-(dimethoxymethylsilylmethyl)cyclohexanamine Chemical compound COC(OC)[SiH2]CNC1CCCCC1 DWYWQJWQNQLGLB-UHFFFAOYSA-N 0.000 description 1
- WUFHQGLVNNOXMP-UHFFFAOYSA-N n-(triethoxysilylmethyl)cyclohexanamine Chemical compound CCO[Si](OCC)(OCC)CNC1CCCCC1 WUFHQGLVNNOXMP-UHFFFAOYSA-N 0.000 description 1
- QRANWKHEGLJBQC-UHFFFAOYSA-N n-(trimethoxysilylmethyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CNC1CCCCC1 QRANWKHEGLJBQC-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MTBVDKSFTCGOTN-UHFFFAOYSA-N octane pentane-2,4-dione tin(4+) Chemical compound [Sn+4].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O.CCCCCCC[CH2-].CCCCCCC[CH2-] MTBVDKSFTCGOTN-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 1
- CZMAXQOXGAWNDO-UHFFFAOYSA-N propane-1,1,2-triol Chemical compound CC(O)C(O)O CZMAXQOXGAWNDO-UHFFFAOYSA-N 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- BOTMPGMIDPRZGP-UHFFFAOYSA-N triethoxy(isocyanatomethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN=C=O BOTMPGMIDPRZGP-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Definitions
- the present invention relates to a (meth)acrylic acid ester-based copolymer having a reactive silicon group, a method for producing the same, and a curable composition containing the copolymer.
- An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon group capable of forming a siloxane bond by a hydrolysis/condensation reaction (hereinafter also referred to as a "reactive silicon group”) can be used even at room temperature. Reacts with moisture, etc. It is known that a rubber-like cured product can be obtained by cross-linking such an organic polymer through a siloxane condensation reaction of reactive silicon groups.
- the polyoxyalkylene polymer having a reactive silicon group has a relatively low viscosity, so it is excellent in workability when preparing or using a blended composition.
- the resulting cured product has a good balance of performance such as mechanical properties, weather resistance, and dynamic durability, it is widely used for applications such as sealants, adhesives, and paints (see Patent Document 1).
- Patent Document 3 a curable resin having a high curing speed and excellent adhesiveness is used for the purpose of eliminating the drawback that the curing speed of one-component moisture-curable adhesives using modified silicone or acrylic-modified silicone is slow.
- an oligomer having a polyether skeleton and having double bonds at both ends, a vinyl monomer such as (meth)acrylic acid ester, and a chain transfer agent are radically polymerized to synthesize a reactive silicon group-containing Graft copolymers are described.
- Polymers having reactive silicon groups are desired to have low viscosity so that they can be easily handled before curing, while exhibiting good physical properties after curing.
- the reactive silicon group-containing graft copolymer described in Patent Document 3 does not have sufficient physical properties after curing, and needs to be improved.
- the present invention provides a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties after curing while having a low viscosity, and a curable composition containing the same. intended to
- the present inventors have conducted intensive studies to solve the above problems, and found that a specific monomer and a chain transfer agent are used as monomer components constituting a reactive silicon group-containing (meth)acrylic acid ester polymer.
- the inventors have found that the above problems can be solved by using a specific ratio, and completed the present invention.
- the first present invention is a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following formula (1), wherein the monomer component constituting the copolymer is , (meth)acrylic acid ester (a1), polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule, and chain transfer agent (a3) having a mercapto group,
- the molar ratio of the polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.06 or more
- the monomer component contains a reactive silicon group and a polymerizable Further containing a monomer (a4) having a saturated group, and / or a (meth) acrylic acid ester copolymer ( A).
- R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
- X represents a hydroxyl group or a hydrolyzable group
- c is 0 or 1.
- the value calculated by the formula: (weight average molecular weight of copolymer (A))/(weight average molecular weight of polyoxyalkylene polymer (a2)) is 0.65 or more.
- the polyoxyalkylene polymer (a2) accounts for 0.08 mol % or more and 6.0 mol % or less in the monomer component.
- the chain transfer agent (a3) having a mercapto group accounts for 0.4 mol % or more and 15 mol % or less in the monomer component.
- the polyoxyalkylene polymer (a2) has a number average molecular weight of 50,000 or less.
- the content of the polyoxyalkylene polymer (a2) is 60% by weight or less in the monomer component.
- the weight average molecular weight of copolymer (A) is 80,000 or less.
- the copolymer (A) has a molecular weight distribution of 3.0 or more and 11.0 or less.
- c in the formula (1) is 0.
- the (meth)acrylic acid ester (a1) is at least one monomer selected from the group consisting of methacrylic acid esters, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate. contains Preferably, among the total amount of the monomer components excluding the polyoxyalkylene-based polymer (a2), the (meth)acrylic acid ester (a1) component, methacrylic acid ester, isobornyl acrylate, and dicyclopentenyl acrylate and at least one monomer selected from the group consisting of dicyclopentanyl acrylate accounts for 60% by weight or more.
- the sulfur atom concentration in the (meth)acrylate copolymer (A) is 700 ppm or more and 20,000 ppm or less.
- the second aspect of the present invention is a (meth)acrylic acid ester copolymer (A) having reactive silicon represented by the following formula (1), wherein the copolymer has two first molecular chains, including a structure bonded via one second molecular chain, both ends of the second molecular chain are respectively bonded to non-terminal sites of the first molecular chain, and the first molecular chain is (meth)acrylic It is composed of a molecular chain of an acid ester polymer, the second molecular chain is composed of a polyoxyalkylene polymer molecular chain, the reactive silicon group is bonded to the first molecular chain, and the first molecular chain is , a structure represented by —SR 3 (wherein S represents a sulfur atom and R 3 represents a hydrocarbon group which may have a reactive silicon group) at either end and the
- the third aspect of the present invention relates to a curable composition containing the (meth)acrylate copolymer (A) or a cured product of the curable composition.
- the fourth aspect of the present invention is a method for producing a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following formula (1), comprising a step of copolymerizing a monomer component Including, the monomer component includes (meth) acrylic acid ester (a1), polyoxyalkylene polymer (a2) having more than one (meth) acryloyl group in the molecule, and a chain having a mercapto group a transfer agent (a3), wherein the molar ratio of the polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.06 or more, and the monomer component comprises Further containing a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group further has a reactive silicon group, (meth) It relates to a method for producing an acrylate copolymer (A).
- R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
- X represents a hydroxyl group or a hydrolyzable group
- c is 0 or 1.
- a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties (e.g., elongation, strength, etc.) after curing while having a low viscosity, and a curability containing the same A composition can be provided.
- the reactive silicon group-containing (meth)acrylic acid ester copolymer according to the present invention contains a block copolymer and can have a relatively low viscosity even if it has a large weight average molecular weight.
- the (meth)acrylic ester-based copolymer (A) has a reactive silicon group represented by the following formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
- —SiR 1 c X 3-c (1) (Wherein, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; c is 0 or 1.)
- the number of carbon atoms in the hydrocarbon group of R 1 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
- Specific examples of R 1 include methyl group, ethyl group, chloromethyl group, methoxymethyl group, N,N-diethylaminomethyl group and the like, preferably methyl group and ethyl group.
- Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group.
- alkoxy groups such as methoxy and ethoxy groups are more preferred, and methoxy and ethoxy groups are particularly preferred, since they are moderately hydrolyzable and easy to handle.
- c is 0 or 1; 0 is preferable because a cured product having a high Young's modulus can be obtained.
- Specific examples of the reactive silicon group possessed by the (meth)acrylate copolymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group.
- dimethoxymethylsilyl group diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like.
- methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- A diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with a high Young's modulus can be obtained. , and a trimethoxysilyl group are more preferred.
- the reactive silicon group equivalent of the (meth)acrylate copolymer (A) is not particularly limited, but is preferably 0.06 mmol/g or more, more preferably 0.08 mmol/g or more, and 0.1 mmol/g. The above is more preferable.
- the reactive silicon group equivalent is preferably 1.0 mmol/g or less, more preferably 0.5 mmol/g or less, and particularly preferably 0.3 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product.
- the (meth)acrylate copolymer (A) comprises at least (meth)acrylate (a1) and a polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule. and a chain transfer agent (a3) having a mercapto group are copolymerized to form a monomer component.
- (meth)acryl means "acryl and/or methacryl”.
- the (meth)acrylic ester-based copolymer (A) has reactive silicon groups by satisfying either one or both of the following two conditions.
- Condition 1 The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group.
- Condition 2 The chain transfer agent (a3) having a mercapto group further has a reactive silicon group.
- the number of reactive silicon groups introduced under Condition 2 is greater than the number of reactive silicon groups introduced under Condition 1.
- the reactive silicon group equivalent introduced under Condition 1 is preferably 0.01 mmol/g or more, more preferably 0.03 mmol/g or more, and even more preferably 0.05 mmol/g or more.
- the reactive silicon group equivalent introduced under Condition 1 is preferably 1.0 mmol/g or less, more preferably 0.5 mmol/g or less.
- the reactive silicon group equivalent introduced under Condition 2 is preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more, and even more preferably 0.5 mmol/g or more.
- the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
- the reactive silicon group equivalent introduced under Condition 1 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. Further, the reactive silicon group equivalent introduced under Condition 1 is preferably 1.8 mmol/g or less, more preferably 1.0 mmol/g or less.
- the reactive silicon group equivalent introduced under Condition 2 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. In addition, the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
- the (meth)acrylic acid ester (a1) is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) ) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)
- the content of the (meth)acrylic acid ester (a1) is 40% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). It is preferably at least 45% by weight, more preferably at least 50% by weight, still more preferably at least 55% by weight, and even more preferably at least 60% by weight. Further, from the viewpoint of durable adhesion, it is preferably 50% by weight or more, more preferably 55% by weight or more, relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). , more preferably 60% by weight or more.
- an alkyl (meth)acrylic acid ester in which the alkyl has 1 to 4 carbon atoms is preferable because a hardened product with high strength can be obtained.
- the (meth)acrylic acid alkyl ester in which the alkyl has 1 to 4 carbon atoms is contained in an amount of 40% by weight or more based on the total amount of the monomer components constituting the (meth)acrylic acid ester-based copolymer (A). preferably 45% by weight or more, and even more preferably 50% by weight or more.
- (Meth)acrylic acid ester (a1) can form a hard polymer chain to obtain a cured product with high strength. It preferably contains at least one monomer selected from the group consisting of dicyclopentanyl.
- the (meth)acrylate (a1) component methacrylate, isobornyl acrylate, dicyclopentenyl acrylate,
- the proportion of at least one monomer selected from the group consisting of dicyclopentanyl acrylate is preferably 60% by weight or more, more preferably 70% by weight or more.
- Polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule The polyoxyalkylene polymer (a2) itself is a polymer, but it is one of the monomers constituting the (meth)acrylate copolymer (A). Since the polyoxyalkylene polymer (a2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (a1). Moreover, since the polyoxyalkylene polymer (a2) has more than one (meth)acryloyl group in one molecule, it can function as a so-called polyfunctional macromonomer.
- the main chain skeleton (second molecular chain described later) of the polyoxyalkylene-based polymer (a2) is the (meth)acrylic acid ester-based copolymer (A), the (meth)acrylic acid ester (a1), etc. It can form a structure that bridges two molecular chains (first molecular chain to be described later) composed of coalescence.
- the polyoxyalkylene polymer (a2) is also referred to as polyfunctional macromonomer (a2).
- the main chain skeleton of the polyfunctional macromonomer (a2) is a polyoxyalkylene polymer.
- the main chain skeleton of the polyfunctional macromonomer (a2) is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, poly Oxypropylene-polyoxybutylene copolymer and the like are included. Among them, polyoxypropylene is preferred.
- the main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but is preferably linear.
- the (meth)acryloyl group possessed by the polyfunctional macromonomer (a2) is preferably represented by the following formula (2).
- CH2 C( R2 )-COO-Z (2)
- R 2 represents hydrogen or a methyl group.
- Z represents the main chain skeleton of the polyfunctional macromonomer (a2).
- the polyfunctional macromonomer (a2) has an average of more than one (meth)acryloyl group in one molecule.
- the average number of (meth)acryloyl groups per molecule of the polyfunctional macromonomer (a2) is preferably 1.1-5, more preferably 1.3-4, and 1.6-2. 5 is more preferred, and 1.8 to 2.0 is particularly preferred.
- the polyfunctional macromonomer (a2) may have only an acryloyl group, may have only a methacryloyl group, or may have both an acryloyl group and a methacryloyl group. You may
- the polyfunctional macromonomer (a2) can have (meth)acryloyl groups at either or both of the molecular chain terminals and side chains of the polyoxyalkylene polymer. From the standpoint of excellent mechanical properties, it is preferred to have it at the end of the molecular chain. In particular, it is particularly preferred that the polyfunctional macromonomer (a2) has a linear main chain skeleton and (meth)acryloyl groups at both ends of the molecular chain.
- the method for synthesizing the polyfunctional macromonomer (a2) is not particularly limited, for example, a polyoxyalkylene polymer having more than one hydroxyl group in the molecule (preferably, a linear A method of preparing a polyoxyalkylene polymer) and introducing a (meth)acryloyl group using the hydroxyl group.
- a polyoxyalkylene polymer having a hydroxyl group is reacted with a compound having an isocyanate group and a (meth)acryloyl group to form a urethane bond.
- (meth)acryloyl groups can be introduced.
- Specific examples of the compound having an isocyanate group and a (meth)acryloyl group include isocyanatoethyl (meth)acrylate, isocyanatopropyl (meth)acrylate, isocyanatobutyl (meth)acrylate, isocyanatohexyl (meth)acrylate, and the like. be done.
- a polyoxyalkylene polymer having hydroxyl groups is reacted with a diisocyanate compound to introduce isocyanate groups into the polymer, and then the hydroxyl groups and (meth ) A (meth)acryloyl group can also be introduced by reacting a compound having an acryloyl group.
- the diisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like.
- the compound having a hydroxyl group and a (meth)acryloyl group include, for example, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acryl acid esters, polypropylene glycol mono(meth)acrylic acid esters, and the like.
- a polyoxyalkylene polymer having a hydroxyl group is reacted with an acid anhydride to introduce a carboxyl group into the polymer, followed by an epoxy group.
- a (meth)acryloyl group can also be introduced by reacting with a compound having a (meth)acryloyl group.
- the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl anhydride.
- Specific examples of the compound having an epoxy group and a (meth)acryloyl group include glycidyl (meth)acrylate.
- Another example of a method for synthesizing the polyfunctional macromonomer (a2) is a method of dehydration condensation of methacrylic acid and acrylic acid on a polyoxyalkylene polymer having hydroxyl groups.
- methacrylic chloride, methacrylic bromide, methacrylic iodide, acrylic acid chloride, acrylic acid bromide, acrylic acid There is a method of reacting iodide or the like.
- the number average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesiveness exhibited by the cured product and the ease of handling of (a2). ,000 or more is more preferable, and 2,000 or more is even more preferable. Also, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, even more preferably 30,000 or less, particularly preferably 15,000 or less, and most preferably 10,000 or less.
- the weight average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesive properties exhibited by the cured product and the ease of handling of (a2). ,000 or more is preferable, and 2,500 or more is more preferable. Also, it is preferably 130,000 or less, more preferably 65,000 or less, even more preferably 60,000 or less, even more preferably 20,000 or less, and most preferably 13,000 or less.
- the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably narrow, specifically less than 2.0. 6 or less is more preferable, 1.5 or less is more preferable, 1.4 or less is still more preferable, and 1.3 or less is particularly preferable.
- the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyfunctional macromonomer (a2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.
- the (meth)acrylic acid ester copolymer (A) is a (meth)acrylic acid ester polymer molecular chain composed of a polymer such as (meth)acrylic acid ester (a1), and a polyfunctional macro It has a polyoxyalkylene polymer molecular chain derived from the monomer (a2).
- the (meth)acrylic acid ester copolymer (A) is a polyoxyalkylene-based It may have a structure in which more than one molecular chain of the (meth)acrylic acid ester-based polymer is bonded to one molecular chain of the polymer.
- the molecular chain of the polyoxyalkylene polymer may be introduced into either the terminal or the side chain (non-terminal portion) of the molecular chain of the (meth)acrylic acid ester polymer. It is preferably introduced into a side chain.
- the polyfunctional macromonomer (a2) has (meth)acryloyl groups at both ends of the molecular chain of the polyoxyalkylene polymer, at both ends of the molecular chain of the polyoxyalkylene polymer, ( An H-type structure in which the molecular chains of the meth)acrylic acid ester-based polymer are bonded can be formed.
- the molecular chain of the polyoxyalkylene-based polymer corresponds to the horizontal bar of H
- the molecular chain of the (meth)acrylic acid ester-based polymer corresponds to the two vertical bars included in H.
- the H-shaped structure will be described later.
- the content of the polyfunctional macromonomer (a2) is preferably 1% by weight or more and 70% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (A). , more preferably 5 wt % or more and 60 wt % or less, and even more preferably 10 wt % or more and 50 wt % or less.
- the content of the polyfunctional macromonomer (a2) is preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 35% by weight or less.
- the content of the polyfunctional macromonomer (a2) is preferably more than 35% by weight.
- the content of the polyfunctional macromonomer (a2) is 0.08 mol% or more and 6.0 mol% or less in the monomer components constituting the (meth)acrylate copolymer (A). It preferably accounts for 0.1 mol % or more and 5.0 mol % or less, and more preferably 0.15 mol % or more and 2.3 mol % or less. Within the above range, the effect of using the polyfunctional macromonomer (a2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylate copolymer (A).
- the average number of polyfunctional macromonomers (a2) per molecule of the (meth)acrylic ester copolymer (A) is obtained by curing the (meth)acrylic ester copolymer (A). From the viewpoint of product strength, it is preferably 0.03 or more and 2.0 or less.
- the lower limit is more preferably 0.04 or more, more preferably 0.05 or more, even more preferably 0.07 or more, and particularly preferably 0.08 or more.
- the upper limit is more preferably 1.5 or less, even more preferably 1.0 or less.
- the average number can be calculated by the following formula.
- a polyfunctional macromonomer (a2) is used by including a chain transfer agent (a3) having a mercapto group in the monomer component constituting the (meth)acrylate copolymer (A). Nevertheless, the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is relatively narrowed, and gelation is suppressed when synthesizing the (meth)acrylic acid ester copolymer (A). can do. In addition, it becomes possible to preferentially synthesize a polymer molecule in which one molecule of the polyfunctional macromonomer (a2) is introduced into one molecule of the (meth)acrylate copolymer (A).
- the chain transfer agent (a3) having a mercapto group may not have a reactive silicon group, but preferably has a reactive silicon group.
- a reactive silicon group can be introduced to the terminal of the molecular chain of the (meth)acrylic acid ester polymer.
- chain transfer agent (a3) having a mercapto group is not particularly limited, examples thereof include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane. , n-dodecylmercaptan, tert-dodecylmercaptan, laurylmercaptan and the like.
- the content of the chain transfer agent (a3) having a mercapto group is 0.1% by weight or more and 11% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (A). It is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.3% by weight or more and 7% by weight or less, and even more preferably 0.5% by weight or more and 5% by weight or less.
- the content of the chain transfer agent (a3) having a mercapto group accounts for 0.1 mol% or more and 20 mol% or less of the monomer components constituting the (meth)acrylate copolymer (A). preferably 0.4 mol% or more and 15 mol% or less, more preferably 0.5 mol% or more and 10 mol% or less, and 0.6 mol% or more and 8 mol% or less is particularly preferred. Within the above range, the effect of using the chain transfer agent (a3) having a mercapto group can be achieved.
- the content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent (a3) having a mercapto group determine the strength of the cured product obtained by curing the (meth)acrylate copolymer (A). is improved, the molar ratio of polyoxyalkylene polymer (a2)/chain transfer agent (a3) having a mercapto group is adjusted to satisfy 0.06 or more. If the molar ratio is less than 0.06, the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the resulting cured product will have insufficient strength.
- the molar ratio is preferably 0.08 or more, more preferably 0.1 or more, still more preferably 0.12 or more, and particularly preferably 0.15 or more.
- the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less.
- the (meth)acrylic acid ester copolymer (A) may have a substituent derived from the chain transfer agent (a3) having a mercapto group (structure represented by —SR 3 described later). Therefore, it may contain sulfur atoms.
- the sulfur atom concentration in the (meth)acrylate copolymer (A) is preferably 700 ppm or more and 20,000 ppm or less, more preferably 1,000 ppm or more and 15,000 ppm or less.
- the method for measuring the sulfur atom concentration is not particularly limited. It can be measured by known elemental analysis methods such as organic elemental analysis and fluorescent X-ray analysis. Further, the sulfur atom concentration is calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (A) and the amount (a3) of the chain transfer agent having a mercapto group. It may be a theoretical value.
- the monomer (a4) having a reactive silicon group and a polymerizable unsaturated group is an arbitrary monomer and may not be used, but is preferably used. By using the monomer (a4), a reactive silicon group can be introduced into the side chain (non-terminal portion) of the molecular chain of the (meth)acrylate polymer.
- Examples of the monomer (a4) having a reactive silicon group and a polymerizable unsaturated group include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-( Compounds having a (meth)acryloxy group and a reactive silicon group, such as meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples include compounds having a vinyl group and a reactive silicon group such as triethoxysilane. These compounds may use only 1 type and may use 2 or more types together.
- the content of the monomer (a4) is 0.1 weight with respect to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A) % or more and 50 wt % or less, more preferably 0.3 wt % or more and 30 wt % or less, and even more preferably 0.5 wt % or more and 20 wt % or less.
- the content of the monomer (a4) is preferably 10% by weight or less, and 5% by weight or less. More preferably, 3% by weight or less is even more preferable.
- the monomer component constituting the (meth)acrylic acid ester copolymer (A) contains another monomer (a5) that does not correspond to any of (a1) to (a4) detailed above. It may contain, or may not contain.
- Other monomers (a5) include (meth)acrylic esters (a1) and monomers (a4) having a reactive silicon group and a polymerizable unsaturated group (meth)acrylic monomers and monomers other than the (meth)acrylic monomer.
- (meth)acrylic acid styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing compounds such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride Vinyl monomers; maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl esters and maleic acid dialkyl esters; fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl esters and fumaric acid dialkyl esters; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide
- the number average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 500 or more and 50,000 or less, preferably 500 or more and 30,000 or less, in terms of polystyrene equivalent molecular weight by GPC measurement. More preferably, 1,000 or more and 10,000 or less are particularly preferable. Among them, the number average molecular weight is preferably 7,000 or less because a (meth)acrylic acid ester copolymer (A) having a low viscosity can be obtained.
- the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 or more and 80,000 or less, and 3,000 or more and 70,000. The following are more preferable, and 5,000 or more and 65,000 or less are particularly preferable. Above all, it is preferably 30,000 or more because good mechanical properties are exhibited.
- the value calculated by the following formula is 0.65 or more. is preferred.
- the fact that the value calculated by the above formula is 0.65 or more means that the average number of introduction of the polyoxyalkylene polymer (a2) in one molecule of the (meth)acrylic acid ester copolymer (A) is large.
- the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A) can be further improved.
- the value calculated by the above formula is more preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.1 or more, and 1.2 or more. It is particularly preferred, and 1.3 or more is most preferred.
- the upper limit is not particularly limited, it is preferably 10 or less, more preferably 5 or less.
- the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (A) low in viscosity, it is 3.0 to 11.0. The following is preferable, 3.2 to 10.0 is more preferable, and 3.4 to 8.0 is even more preferable.
- the molecular weight distribution of the (meth)acrylate copolymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
- the (meth)acrylate copolymer (A) may contain a triblock copolymer.
- the triblock copolymer comprises a structure in which two first molecular chains are linked via one second molecular chain.
- the first molecular chain is composed of a (meth)acrylic ester-based polymer molecular chain
- the second molecular chain is composed of a polyoxyalkylene-based polymer molecular chain.
- the first molecular chain is a molecular chain formed by copolymerization of (a1), (meth)acryloyl groups in (a2), (a3), optional (a4), and optional other monomers. .
- a reactive silicon group is attached to this first molecular chain.
- the chain transfer agent (a3) having a mercapto group has a reactive silicon group
- a reactive silicon group is bonded to the end of the first molecular chain, and a monomer having a reactive silicon group and a polymerizable unsaturated group
- a4 is used, a reactive silicon group is attached to the non-terminal portion of the first molecular chain.
- the second molecular chain corresponds to the main chain skeleton of the polyoxyalkylene polymer in the polyfunctional macromonomer (a2).
- the bonding method of two first molecular chains and one second molecular chain is different from that of ordinary ABA-type triblock copolymers, and both ends of the second molecular chain are respectively non-terminal sites of the first molecular chain.
- the triblock copolymer comprises an H-type structure, where two vertical bars in H correspond to two first molecular chains and one horizontal bar in H corresponds to one second molecular chain. It corresponds to a molecular chain.
- the (meth)acrylic acid ester-based copolymer (A) is not limited to a triblock copolymer with an H-type structure, and in addition to a triblock copolymer with an H-type structure, It may contain a block copolymer having Block copolymers having such other structures include, for example, block copolymers having a structure in which three first molecular chains are bonded via two second molecular chains.
- the first molecular chain and the second molecular chain have an ester bond derived from the (meth)acryloyl group in the polyfunctional macromonomer (a2) (that is, an ester bond corresponding to the ester bond in the formula (2)). are connected through
- a hard polymer refers to a polymer with a high glass transition temperature.
- a soft polymer refers to a polymer with a low glass transition temperature.
- the monomer components constituting the first molecular chain include methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and , and dicyclopentanyl acrylate.
- the ratio of the monomers to the total amount of monomer components constituting the first molecular chain is preferably 60% by weight or more, more preferably 70% by weight or more.
- the first molecular chain is a molecular chain formed by reacting the chain transfer agent (a3) having a mercapto group, at either end of the first molecular chain, as a substituent derived from (a3) , —SR 3 .
- S represents a sulfur atom
- R3 represents a hydrocarbon group which may have a reactive silicon group.
- the hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and the like.
- the reactive silicon group is a reactive silicon group represented by formula (1) described above. Specific examples of R 3 include reactive silicon group-containing methyl group, reactive silicon group-containing propyl group, n-dodecyl group, tert-dodecyl group, lauryl group and the like.
- the molar ratio of the polyoxyalkylene polymer to the —SR 3 is 0.06 or more. If the molar ratio is less than 0.06, the weight average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the resulting cured product will have insufficient strength.
- the molar ratio is preferably 0.08 or more, more preferably 0.1 or more, still more preferably 0.12 or more, and particularly preferably 0.15 or more. Although the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less.
- the (meth)acrylate copolymer (A) can be produced by polymerizing the above monomer components.
- the polymerization method is not particularly limited, but may be general free radical polymerization. According to the present embodiment, although it is a free radical polymerization, the polymerization can be controlled, and the (meth)acrylic acid ester copolymer (A), which is a block copolymer, can be produced. , its molecular weight distribution can be relatively narrow.
- Polymerization initiators that can be used in the free radical polymerization include, for example, 2,2′-azobis(2-methylbutyronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2 '-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis [N- (2-propenyl) -2- methyl propionamide], 1,1'-azobis (cyclohexane-1-carbonitrile) and other azo compounds; benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, para diacyl peroxides such as chlorobenzoyl peroxide and di(3,5,5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2
- solvents that can be used in the free radical polymerization include aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; hexane, Aliphatic hydrocarbon solvents such as heptane, octane, cyclohexane, methylcyclohexane; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate, and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dimethyl carbonate, diethyl carbonate, etc.
- aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethy
- alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol.
- alcohol compounds are preferable because they have a narrow molecular weight distribution.
- Aromatic solvents are preferred because of their high dissolving power.
- Aliphatic hydrocarbon solvents are preferred because of their low odor.
- the molecular weight distribution of the (meth)acrylate copolymer (A) is affected by the amount of the chain transfer agent (a3) added and the solvent. When the amount of the chain transfer agent (a3) added is 2% by weight or less, it is greatly affected by the type of solvent.
- isobutanol is preferably used as the solvent.
- an aromatic hydrocarbon solvent it is preferable to use an aromatic hydrocarbon solvent as the solvent.
- the (meth)acrylic acid ester copolymer (A) uses a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, or reacts in addition to a mercapto group
- a chain transfer agent (a3) which additionally has reactive silicon groups, it will have reactive silicon groups. Both methods may be used in combination.
- a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group a reactive silicon group is randomly introduced into the side chain of the molecular chain of the (meth)acrylic acid ester polymer. can be done.
- a chain transfer agent (a3) further having a reactive silicon group in addition to a mercapto group it is possible to introduce a reactive silicon group to the end of the molecular chain of the (meth)acrylate polymer. can.
- the following methods can be used in combination.
- a method of reacting a compound having a silicon group is used.
- a reaction method and the like can be exemplified.
- (ii) A method of modifying terminal functional groups of a (meth)acrylic acid ester-based copolymer synthesized by a living radical polymerization method to introduce a reactive silicon group.
- a (meth)acrylic acid ester-based copolymer obtained by a living radical polymerization method is easy to introduce a functional group to the polymer terminal, and by modifying this, a reactive silicon group can be introduced to the polymer terminal.
- Examples of the compound having a functional group that reacts with group V and a reactive silicon group used in method (i) include 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
- any modification reaction can be used.
- This embodiment also relates to a curable composition containing a (meth)acrylate copolymer (A).
- the curable composition may contain only the (meth)acrylic acid ester copolymer (A) as the reactive silicon group-containing polymer, or may contain the (meth)acrylic acid ester copolymer (A).
- other reactive silicon group-containing polymers may be contained.
- the curable composition according to the present embodiment promotes the reaction of condensing the reactive silicon groups of the (meth)acrylic acid ester-based copolymer (A), and for the purpose of chain extension or crosslinking of the polymer, silanol condensation It preferably contains a catalyst.
- silanol condensation catalysts examples include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
- organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds.
- reaction product with dibutyltin oxide and phthalate ester dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), dioctyltin distearate, dioctyltin oxide, a reaction product of dioctyltin oxide and a silicate compound, and the like.
- carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
- carboxylic acid metal salt the following carboxylic acid and various metals can be combined.
- amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine compounds;
- carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
- alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum ethylacetate
- titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum ethylacetate
- Aluminum compounds such as acetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), and the like.
- fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
- the silanol condensation catalyst may be used in combination of two or more different catalysts.
- the combined use of the amine compound and carboxylic acid, or the combined use of the amine compound and alkoxy metal has the effect of improving reactivity. may be obtained.
- the amount used is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer (A), and 0.01 to 15 parts by weight is more preferred, and 0.01 to 10 parts by weight is particularly preferred.
- the curable composition according to the present embodiment includes a (meth) acrylic acid ester copolymer (A), and an optional silanol condensation catalyst, as additives, a filler, an adhesion imparting agent, and an anti-sagging agents, antioxidants, light stabilizers, UV absorbers, and other resins.
- the curable composition according to the present embodiment may contain various additives as necessary for the purpose of adjusting various physical properties of the composition or its cured product.
- additives examples include plasticizers, solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, agents, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents, and the like.
- the curable composition according to this embodiment can contain a filler.
- Such fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, wet silica, anhydrous silica. Acid, hydrous silicic acid, alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, filament and the like.
- the amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
- Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.
- the curable composition according to this embodiment can contain an adhesion imparting agent.
- a silane coupling agent or a reactant of the silane coupling agent can be used as the adhesion imparting agent.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
- Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used.
- the adhesiveness-imparting agent may be used alone or in combination of two or more.
- the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
- plasticizer can be added to the curable composition according to the present embodiment.
- plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl ole
- polymer plasticizer can be used.
- polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
- a plasticizer may be used individually and may use 2 or more types together.
- the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A). More preferred.
- Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
- the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. .
- the above solvents or diluents may be used alone or in combination of two or more.
- the curable composition according to the present embodiment may contain an anti-sagging agent as necessary to prevent sagging and improve workability.
- the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
- the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A).
- the curable composition according to this embodiment can contain an antioxidant (antiaging agent).
- an antioxidant can enhance the weather resistance of the cured product.
- antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
- the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
- the curable composition according to this embodiment can contain a light stabilizer.
- a light stabilizer can prevent photo-oxidative deterioration of the cured product.
- Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.
- the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
- the curable composition according to this embodiment can contain an ultraviolet absorber.
- the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
- UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazoles are particularly preferred. Specific examples include commercial names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
- the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
- a physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition according to the present embodiment, if necessary.
- the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
- arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
- the physical property modifiers may be used alone or in combination of two or more.
- a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without exacerbating the stickiness of the surface of the cured product.
- Compounds that generate trimethylsilanol are particularly preferred.
- examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups.
- Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
- the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
- a tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes.
- the tackifying resin there is no particular limitation, and those commonly used can be used.
- terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
- petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
- the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the (meth)acrylate copolymer (A). Parts by weight are more preferred.
- a compound containing an epoxy group can be used in the curable composition according to the present embodiment.
- the use of a compound having an epoxy group can enhance the restorability of the cured product.
- compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
- the epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the (meth)acrylate copolymer (A).
- a photocurable substance can be used in the curable composition according to the present embodiment.
- a photocurable substance When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
- Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
- the amount of the photocurable substance used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A), and more preferably 0.5 to 10 parts by weight. preferable.
- oxygen-curable substance can be used in the curable composition according to this embodiment.
- oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
- Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
- silicone resins 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- liquid polymers These may be used alone or in combination of two or more.
- the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A). part is more preferred.
- oxygen-curable substances are preferably used in combination with photo-curable substances.
- Epoxy resin can be used in combination with the curable composition according to the present embodiment.
- a composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles.
- epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
- a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present embodiment.
- the epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.
- the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
- the curable composition according to the present embodiment is preferably prepared as a one-component type in which all the ingredients are preliminarily blended, sealed and stored, and cured by moisture in the air after application.
- the curable composition is of the one-component type, all ingredients are blended in advance. Therefore, ingredients containing water are dehydrated and dried before use, or dehydrated by decompression during compounding and kneading. is preferred.
- the heat drying method is suitable for solid substances such as powder, and the dehydration method under reduced pressure or the dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is suitable for liquid substances.
- a small amount of an isocyanate compound may be blended to react the isocyanate groups with water to dehydrate.
- An oxazolidine compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be blended and reacted with water for dehydration.
- the storage stability can be further improved by adding lower alcohols such as methanol and ethanol, and alkoxysilane compounds.
- alkoxysilane compounds include methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane. ethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and the like.
- the amount of the dehydrating agent, particularly the alkoxysilane compound used, is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the (meth)acrylate copolymer (A). more preferred.
- the method for preparing the curable composition according to this embodiment is not particularly limited.
- the above components are blended and kneaded at room temperature or under heat using a mixer, roll, kneader, etc., or a small amount of an appropriate solvent is used to dissolve and mix the above components. methods can be employed.
- the curable composition according to the present embodiment includes sealing materials for buildings, ships, automobiles, roads, etc., adhesives, molding agents, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spraying materials, It can be used as a coating film waterproofing agent.
- the curable composition is a sealant or an adhesive. It is more preferable to use as
- the curable composition according to the present embodiment includes electrical and electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulating coating materials for electric wires and cables, elastic adhesives, contact adhesives, and spray seals. materials, crack repair materials, adhesives for tiling, powder coatings, casting materials, medical rubber materials, medical adhesives, sealing materials for medical equipment, food packaging materials, joint sealing materials for exterior materials such as sizing boards , coating materials, primers, conductive materials for shielding electromagnetic waves, thermally conductive materials, hot-melt materials, potting agents for electrical and electronic devices, films, gaskets, various molding materials, rust prevention of wire glass and laminated glass edge faces (cut parts) ⁇ It can be used for various purposes such as waterproof sealing materials, liquid sealants used in automotive parts, electrical parts, and various machine parts.
- electrical and electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulating coating materials for electric wires and cables, elastic adhesives, contact adhesives, and spray seals. materials, crack repair
- the cured product of the curable composition according to the present embodiment can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings by using alone or in combination with a primer.
- the article can also be used as a sealing composition or adhesive composition.
- the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for masonry, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
- Adhesives, vehicle panel adhesives, electrical/electronic/precision equipment assembly adhesives, direct glazing sealing materials, double glazing sealing materials, SSG construction method sealing materials, or building working joint sealing materials is also available.
- the number average molecular weight and weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.
- Liquid delivery system Tosoh HLC-8220GPC
- Column TSK-GEL H type manufactured by Tosoh Solvent: THF
- Molecular weight Polystyrene equivalent Measurement temperature: 40°C
- sulfur atom concentration is a theoretical value calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (A) and the amount of the chain transfer agent (a3) having a mercapto group. be.
- a polymer having acryloyl groups at both ends (that is, having about two acryloyl groups in one polymer molecule), having a number average molecular weight of 4,020 and a weight average molecular weight of 4,860
- An oxyalkylene polymer (a2-1) was obtained.
- Synthesis example 2 Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal group: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to have hydroxyl groups at both ends. , a number average molecular weight of 21,100 (termed molecular weight of terminal groups: 13,600) and a molecular weight distribution Mw/Mn of 1.21.
- the solution was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
- An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) having a molecular weight of 470 (GPC) was obtained.
- the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.070 mmol/g, a reactive silicon group equivalent weight of 0.42 mmol/g, and a sulfur atom concentration of 10,941 ppm.
- an isobutanol solution (solid content: 60%) of the reactive silicon group-containing (meth)acrylic acid ester copolymer (A-2) was obtained.
- the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.12 mmol/g, a reactive silicon group equivalent weight of 0.34 mmol/g, and a sulfur atom concentration of 10,291 ppm.
- the solution was added dropwise over 5 hours. Further, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
- An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylate copolymer (A-3) having a molecular weight of 910 (GPC) was obtained.
- the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.094 mmol/g, a reactive silicon group equivalent weight of 0.53 mmol/g, and a sulfur atom concentration of 15,961 ppm.
- a mixed solution dissolved in .9 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 9.5 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
- An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylate copolymer (A-5) having a molecular weight of 120 (GPC) was obtained.
- the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.012 mmol/g, a reactive silicon group equivalent weight of 0.12 mmol/g, and a sulfur atom concentration of 2,402 ppm.
- a mixed solution of 0.2 parts by weight of 2,2′-azobis(2-methylbutyronitrile) dissolved in 5.3 parts by weight of SOLVESSO 100 was added and polymerized at 110° C. for 2 hours to obtain a number average molecular weight of 5,360.
- a solution (solid content: 60%) of reactive silicon group-containing (meth)acrylic acid ester copolymer (A-9) having (GPC molecular weight) was obtained.
- the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.0091 mmol/g, a reactive silicon group equivalent weight of 0.18 mmol/g, and a sulfur atom concentration of 3,912 ppm.
- the dissolved mixed solution was added dropwise over 5 hours. Further, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
- An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) having a molecular weight of 980 (GPC) was obtained.
- the solid content of the solution has a reactive silicon group equivalent of 0.72 mmol/g and a sulfur atom concentration of 10,948 ppm.
- An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-6) having a GPC molecular weight of 770 was obtained.
- the solid content of the solution has a reactive silicon group equivalent of 0.20 mmol/g and a sulfur atom concentration of 5,716 ppm.
- a polyfunctional macromonomer (a2) which is a polyoxyalkylene polymer having more than one (meth)acryloyl group in one molecule, and a mercapto group
- Reactive silicon group-containing (meth)acrylic acid ester copolymers (A-1) to (A-3) could be synthesized by copolymerizing both chain transfer agents (a3) possessed.
- These copolymers (A-1) to (A-3) include block copolymers formed by copolymerizing the polyfunctional macromonomer (a2) with butyl acrylate or the like.
- the (meth)acrylate copolymer (P-2) of Comparative Example 2 was synthesized without using the polyfunctional macromonomer (a2) and is a random copolymer. From Table 1, the (meth) acrylic ester copolymers (A-1) to (A-3) have a weight average molecular weight compared to the (meth) acrylic ester copolymer (P-2). It can be seen that the viscosity relative to (Mw) is low. For example, (A-3) has a viscosity of about 1/4 that of (P-2), although it has a weight average molecular weight slightly higher than that of (P-2). In addition, although (A-2) has a weight average molecular weight as high as about three times that of (P-2), its viscosity is almost the same.
- the (meth)acrylate copolymer (P-3) of Comparative Example 3 is an allyl group-containing polyoxyalkylene polymer (p -1), judging from its weight average molecular weight (Mw), copolymerization of (p-1) hardly progressed. That is, the (meth)acrylic acid ester copolymers (A-1) to (A-3) have low viscosities despite the progress of copolymerization of the polyfunctional macromonomer (a2). I understand.
- Neostan U-20 dibutyltin dibutylmalate manufactured by Nitto Kasei Co., Ltd.
- a sheet of The obtained sheet was subjected to hardening and curing for 2 weeks under conditions of 23° C. and 50% RH.
- a strip test piece of 70 mm ⁇ 10 mm was cut out from the obtained sheet, and the tensile physical properties were measured at 23° C. with the distance between grips set to 40 mm.
- the cured products obtained from the (meth)acrylic acid ester copolymers (A-4) to (A-7) of Examples 4 to 7 were chain transfer agents (a3 ) compared to the cured product obtained from the (meth)acrylic ester-based copolymer (P-4) of Comparative Example 4 in which the ratio of the polyfunctional macromonomer (a2) used is small, 30% modulus (M30) , tensile strength (TB) and Young's modulus.
- the (meth)acrylic acid ester copolymer (P-5) of Comparative Example 5 has a monomer ( The amount of a4) used is increased to increase the reactive silicon group equivalent.
- Comparative Example 5 had slightly higher values of tensile strength and Young's modulus, but significantly lower elongation.
- Examples 4 to 6 have larger values of tensile strength and Young's modulus than Comparative Example 5, and also have larger elongation. From the (meth)acrylic acid ester copolymer (P-6) of Comparative Example 6 synthesized without using the polyfunctional macromonomer (a2), the cured product was too soft and a test piece could not be produced. rice field.
- the cured products obtained from the (meth)acrylate copolymers (A-8) and (A-9) of Examples 8 and 9 have high Young's moduli.
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Abstract
Description
しかし、特許文献3に記載の反応性ケイ素基含有グラフト共重合体は、硬化後の物性が十分なものではなく、改善する必要があった。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。)
好ましくは、式:(共重合体(A)の重量平均分子量)/(ポリオキシアルキレン系重合体(a2)の重量平均分子量)で算出される値が、0.65以上である。
好ましくは、ポリオキシアルキレン系重合体(a2)が、前記単量体成分中0.08モル%以上6.0モル%以下を占める。
好ましくは、メルカプト基を有する連鎖移動剤(a3)が、前記単量体成分中0.4モル%以上15モル%以下を占める。
好ましくは、ポリオキシアルキレン系重合体(a2)の数平均分子量が50,000以下である。
好ましくは、ポリオキシアルキレン系重合体(a2)の含有量が、前記単量体成分中60重量%以下である。
好ましくは、共重合体(A)の重量平均分子量が80,000以下である。
好ましくは、共重合体(A)の分子量分布が3.0以上11.0以下である。
好ましくは、前記式(1)におけるcが0である。
好ましくは、(メタ)アクリル酸エステル(a1)は、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも1種の単量体を含有する。
好ましくは、ポリオキシアルキレン系重合体(a2)を除く前記単量体成分の総量のうち、(メタ)アクリル酸エステル(a1)成分である、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも1種の単量体が占める割合が60重量%以上である。
好ましくは、(メタ)アクリル酸エステル系共重合体(A)中の硫黄原子濃度が700ppm以上20,000ppm以下である。
第二の本発明は、下記式(1)に示す反応性ケイ素を有する(メタ)アクリル酸エステル系共重合体(A)であって、前記共重合体は、2つの第一分子鎖が、1つの第二分子鎖を介して結合している構造を含み、第二分子鎖の両末端がそれぞれ、第一分子鎖の非末端部位に結合しており、第一分子鎖は(メタ)アクリル酸エステル系重合体の分子鎖から構成され、第二分子鎖はポリオキシアルキレン系重合体の分子鎖から構成され、前記反応性ケイ素基は、第一分子鎖に結合し、第一分子鎖は、いずれかの末端に、-S-R3(式中、Sは硫黄原子を表し、R3は、前記反応性ケイ素基を有していてもよい炭化水素基を表す)で表される構造を有し、前記-S-R3に対する前記ポリオキシアルキレン系重合体のモル比が、0.06以上である、(メタ)アクリル酸エステル系共重合体(A)に関する。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。)
本発明の第三は、前記(メタ)アクリル酸エステル系共重合体(A)を含む硬化性組成物、又は、該硬化性組成物の硬化物に関する。
本発明の第四は、下記式(1)に示す反応性ケイ素基を有する(メタ)アクリル酸エステル系共重合体(A)の製造方法であって、単量体成分を共重合する工程を含み、前記単量体成分が、(メタ)アクリル酸エステル(a1)、(メタ)アクリロイル基を分子内に1つより多く有するポリオキシアルキレン系重合体(a2)、及び、メルカプト基を有する連鎖移動剤(a3)、を含有し、ポリオキシアルキレン系重合体(a2)/メルカプト基を有する連鎖移動剤(a3)のモル比が、0.06以上であり、並びに前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体(a4)をさらに含有し、及び/又は、メルカプト基を有する連鎖移動剤(a3)が、反応性ケイ素基をさらに有する、(メタ)アクリル酸エステル系共重合体(A)の製造方法に関する。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。)
(メタ)アクリル酸エステル系共重合体(A)は、下記式(1)で表される反応性ケイ素基を分子鎖末端及び/又は側鎖(非末端部位)に有する。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。)
条件1:前記単量体成分は、さらに、反応性ケイ素基と重合性不飽和基を有する単量体(a4)を含有する。
条件2:メルカプト基を有する連鎖移動剤(a3)が、反応性ケイ素基をさらに有する。
(メタ)アクリル酸エステル(a1)としては特に限定されないが、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸n-ヘプチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸フェニル、(メタ)アクリル酸トルイル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸3-メトキシブチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸のエチレンオキシド付加物、(メタ)アクリル酸2,2,2-トリフルオロエチル、(メタ)アクリル酸3,3,3-トリフルオロプロピル、(メタ)アクリル酸3,3,4,4,4-ペンタフルオロブチル、(メタ)アクリル酸2-パーフルオロエチル-2-パーフルオロブチルエチル、(メタ)アクリル酸トリフルオロメチル、(メタ)アクリル酸パーフルオロエチル、(メタ)アクリル酸ビス(トリフルオロメチル)メチル、(メタ)アクリル酸2-トリフルオロメチル-2-パーフルオロエチルエチル、(メタ)アクリル酸2-パーフルオロヘキシルエチル、(メタ)アクリル酸2-パーフルオロデシルエチル、(メタ)アクリル酸2-パーフルオロヘキサデシルエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸クロロエチル、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸2-アミノエチル等が挙げられる。1種類のみを使用してもよいし、2種以上を併用してもよい。
(メタ)アクリル酸エステル(a1)としては(メタ)アクリル酸アルキルエステルが好ましい。
ポリオキシアルキレン系重合体(a2)はこれ自体が重合体であるが、(メタ)アクリル酸エステル系共重合体(A)を構成する単量体の1つである。ポリオキシアルキレン系重合体(a2)は(メタ)アクリロイル基を有することによって、(メタ)アクリル酸エステル(a1)など他の単量体と共重合することができる。しかも、ポリオキシアルキレン系重合体(a2)は(メタ)アクリロイル基を1分子内に1つより多く有するため、いわゆる多官能性マクロモノマーとして機能することができる。ポリオキシアルキレン系重合体(a2)の主鎖骨格(後述する第二分子鎖)は、(メタ)アクリル酸エステル系共重合体(A)において、(メタ)アクリル酸エステル(a1)などの重合体から構成される2本の分子鎖(後述する第一分子鎖)を架橋する構造を形成し得る。以下、ポリオキシアルキレン系重合体(a2)を多官能性マクロモノマー(a2)ともいう。
CH2=C(R2)-COO-Z (2)
(式中、R2は、水素またはメチル基を表す。Zは、多官能性マクロモノマー(a2)の主鎖骨格を表す。)
前記イソシアネート基と(メタ)アクリロイル基を有する化合物の具体例としては、例えば、イソシアネートエチル(メタ)アクリレート、イソシアネートプロピル(メタ)アクリレート、イソシアネートブチル(メタ)アクリレート、イソシアネートヘキシル(メタ)アクリレート等が挙げられる。
前記ジイソシアネート化合物の具体例としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート等が挙げられる。
前記水酸基と(メタ)アクリロイル基を有する化合物の具体例としては、例えば、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシエチル、ポリエチレングリコールモノ(メタ)アクリル酸エステル、ポリプロピレングリコールモノ(メタ)アクリル酸エステル等が挙げられる。
前記酸無水物の具体例としては、例えば、無水コハク酸、無水マレイン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水メチルヘキサヒドロフタル酸、無水メチルハイミック酸、無水トリメリット酸、無水メチルナジック酸、ドデシル無水コハク酸等が挙げられる。
前記エポキシ基と(メタ)アクリロイル基を有する化合物の具体例としては、例えば、(メタ)アクリル酸グリシジル等が挙げられる。
式:(メタ)アクリル酸エステル系共重合体(A)の数平均分子量(g/mol)/((メタ)アクリル酸エステル系共重合体(A)の重量(g)/(ポリオキシアルキレン系重合体(a2)のモル数))
(メタ)アクリル酸エステル系共重合体(A)を構成する単量体成分に、メルカプト基を有する連鎖移動剤(a3)を含めることによって、多官能性マクロモノマー(a2)を使用しているにも関わらず、(メタ)アクリル酸エステル系共重合体(A)の分子量分布を比較的狭くし、かつ(メタ)アクリル酸エステル系共重合体(A)を合成する時のゲル化を抑制することができる。また、(メタ)アクリル酸エステル系共重合体(A)の1分子に多官能性マクロモノマー(a2)が1分子導入された重合体分子を優先的に合成することが可能となる。
反応性ケイ素基と重合性不飽和基を有する単量体(a4)は、任意の単量体であり、使用しなくともよいが、使用することが好ましい。単量体(a4)を使用することによって、(メタ)アクリル酸エステル系重合体の分子鎖の側鎖(非末端部位)に反応性ケイ素基を導入することができる。
(メタ)アクリル酸エステル系共重合体(A)を構成する単量体成分は、以上で詳述した(a1)~(a4)のいずれにも該当しない他の単量体(a5)を含有するものであってもよいし、含有しないものであってもよい。
他の単量体(a5)としては、(メタ)アクリル酸エステル(a1)や反応性ケイ素基と重合性不飽和基を有する単量体(a4)に該当しない(メタ)アクリル系単量体や、該(メタ)アクリル系単量体以外の単量体が挙げられる。具体的には、(メタ)アクリル酸;スチレン、ビニルトルエン、α-メチルスチレン、クロロスチレン、スチレンスルホン酸等のスチレン系単量体;パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニル単量体;マレイン酸、無水マレイン酸、マレイン酸モノアルキルエステル、マレイン酸ジアルキルエステル等のマレイン酸およびその誘導体;フマル酸、フマル酸モノアルキルエステル、フマル酸ジアルキルエステル等のフマル酸およびその誘導体;マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系単量体;酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル系単量体;エチレン、プロピレン等のオレフィン系単量体;ブタジエン、イソプレン等の共役ジエン系単量体;(メタ)アクリルアミド;(メタ)アクリロニトリル;塩化ビニル、塩化ビニリデン、塩化アリル、アリルアルコール、エチルビニルエーテル、ブチルビニルエーテル等のビニル系単量体が挙げられる。これら他の単量体は1種のみを使用してもよく、2種以上を併用してもよい。
式:(共重合体(A)の重量平均分子量)/(ポリオキシアルキレン系重合体(a2)の重量平均分子量)
前記式で算出される値が0.65以上であるということは、(メタ)アクリル酸エステル系共重合体(A)1分子中のポリオキシアルキレン系重合体(a2)の平均導入個数が多いことを意味しており、(メタ)アクリル酸エステル系共重合体(A)を硬化させて得られる硬化物の強度がより向上し得る。
硬化物の強度の観点から、前記式で算出される値は、0.8以上であることがより好ましく、1.0以上がさらに好ましく、1.1以上がより更に好ましく、1.2以上が特に好ましく、1.3以上が最も好ましい。上限は特に限定されないが、10以下が好ましく、5以下がより好ましい。
一方、第二分子鎖は、多官能性マクロモノマー(a2)中のポリオキシアルキレン系重合体の主鎖骨格にあたる。
(メタ)アクリル酸エステル系共重合体(A)は、前記単量体成分を重合することによって製造できる。その重合方法は特に限定されないが、一般的なフリーラジカル重合であってよい。本実施形態によると、フリーラジカル重合であるにも関わらず、重合の制御が可能で、ブロック共重合体である(メタ)アクリル酸エステル系共重合体(A)を製造することができ、しかも、その分子量分布を比較的狭くすることができる。
(i)反応性官能基(V基)を有する単量体を(メタ)アクリル酸エステル(a1)などと共重合した後、得られた共重合体に、V基に反応する官能基と反応性ケイ素基を有する化合物を反応させる方法。具体的には、アクリル酸2-ヒドロキシエチルを共重合した後、反応性ケイ素基を有するイソシアネートシラン化合物を反応させる方法や、アクリル酸グリシジルを共重合した後、反応性ケイ素基を有するアミノシラン化合物を反応させる方法などが例示できる。
(ii)リビングラジカル重合法によって合成した(メタ)アクリル酸エステル系共重合体の末端官能基を変性して、反応性ケイ素基を導入する方法。リビングラジカル重合法によって得られる(メタ)アクリル酸エステル系共重合体は重合体末端に官能基を導入しやすく、これを変性することで重合体末端に反応性ケイ素基を導入することができる。
本実施形態は、(メタ)アクリル酸エステル系共重合体(A)を含む硬化性組成物にも関する。該硬化性組成物は、反応性ケイ素基含有重合体として、(メタ)アクリル酸エステル系共重合体(A)のみを含有するものであってもよいし、(メタ)アクリル酸エステル系共重合体(A)に加えて、他の反応性ケイ素基含有重合体を含有するものであってもよい。
本実施形態に係る硬化性組成物は、(メタ)アクリル酸エステル系共重合体(A)の反応性ケイ素基を縮合させる反応を促進し、重合体を鎖延長または架橋させる目的で、シラノール縮合触媒を含有することが好ましい。
本実施形態に係る硬化性組成物は、(メタ)アクリル酸エステル系共重合体(A)、及び、任意のシラノール縮合触媒の他に、添加剤として、充填剤、接着性付与剤、タレ防止剤、酸化防止剤、光安定剤、紫外線吸収剤、その他の樹脂などを含有しても良い。また、本実施形態に係る硬化性組成物は、該組成物又はその硬化物の諸物性の調整を目的として、必要に応じて各種添加剤を含有してもよい。このような添加物の例としては、例えば、可塑剤、溶剤、希釈剤、光硬化性物質、酸素硬化性物質、表面性改良剤、シリケート、硬化性調整剤、ラジカル禁止剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、防かび剤、難燃剤、発泡剤などが挙げられる。
本実施形態に係る硬化性組成物は、充填剤を含有することができる。そのような充填剤としては、重質炭酸カルシウム、膠質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、クレー、タルク、酸化チタン、ヒュームドシリカ、沈降性シリカ、結晶性シリカ、溶融シリカ、湿式シリカ、無水ケイ酸、含水ケイ酸、アルミナ、カーボンブラック、酸化第二鉄、アルミニウム微粉末、酸化亜鉛、活性亜鉛華、PVC粉末、PMMA粉末、ガラス繊維、フィラメント等が挙げられる。
本実施形態に係る硬化性組成物は、接着性付与剤を含有することができる。接着性付与剤としては、シランカップリング剤、シランカップリング剤の反応物を使用することができる。
本実施形態に係る硬化性組成物には、可塑剤を添加することができる。可塑剤の具体例としては、ジブチルフタレート、ジイソノニルフタレート(DINP)、ジヘプチルフタレート、ジ(2-エチルヘキシル)フタレート、ジイソデシルフタレート(DIDP)、ブチルベンジルフタレートなどのフタル酸エステル化合物;ビス(2-エチルヘキシル)-1,4-ベンゼンジカルボキシレートなどのテレフタル酸エステル化合物;1,2-シクロヘキサンジカルボン酸ジイソノニルエステルなどの非フタル酸エステル化合物;アジピン酸ジオクチル、セバシン酸ジオクチル、セバシン酸ジブチル、コハク酸ジイソデシル、アセチルクエン酸トリブチルなどの脂肪族多価カルボン酸エステル化合物;オレイン酸ブチル、アセチルリシノール酸メチルなどの不飽和脂肪酸エステル化合物;アルキルスルホン酸フェニルエステル;リン酸エステル化合物;トリメリット酸エステル化合物;塩素化パラフィン;アルキルジフェニル、部分水添ターフェニルなどの炭化水素系油;プロセスオイル;エポキシ化大豆油、エポキシステアリン酸ベンジルなどのエポキシ可塑剤等が挙げられる。
本実施形態に係る硬化性組成物には溶剤または希釈剤を添加することができる。溶剤及び希釈剤としては、特に限定されないが、脂肪族炭化水素、芳香族炭化水素、脂環族炭化水素、ハロゲン化炭化水素、アルコール、エステル、ケトン、エーテルなどを使用することができる。溶剤または希釈剤を使用する場合、組成物を屋内で使用した時の空気への汚染の問題から、溶剤の沸点は、150℃以上が好ましく、200℃以上がより好ましく、250℃以上が特に好ましい。上記溶剤または希釈剤は単独で用いてもよく、2種以上併用してもよい。
本実施形態に係る硬化性組成物は、必要に応じてタレを防止し、作業性を良くするために、タレ防止剤を含有しても良い。タレ防止剤としては特に限定されないが、例えば、ポリアミドワックス類;水添ヒマシ油誘導体類;ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸バリウム等の金属石鹸類等が挙げられる。これらタレ防止剤は単独で用いてもよく、2種以上併用してもよい。
本実施形態に係る硬化性組成物は、酸化防止剤(老化防止剤)を含有することができる。酸化防止剤を使用すると硬化物の耐候性を高めることができる。酸化防止剤としてはヒンダードフェノール系、モノフェノール系、ビスフェノール系、ポリフェノール系などが例示できる。酸化防止剤の具体例は特開平4-283259号公報や特開平9-194731号公報にも記載されている。
本実施形態に係る硬化性組成物は、光安定剤を含有することができる。光安定剤を使用すると硬化物の光酸化劣化を防止できる。光安定剤としては、ベンゾトリアゾール系、ヒンダードアミン系、ベンゾエート系化合物等が例示できるが、特にヒンダードアミン系が好ましい。
本実施形態に係る硬化性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤を使用すると硬化物の表面耐候性を高めることができる。紫外線吸収剤としては、ベンゾフェノン系、ベンゾトリアゾール系、サリチレート系、置換アクリロニトリル系、金属キレート系化合物等が例示できる。特にベンゾトリアゾール系が好ましい。具体例としては、市販名チヌビンP、チヌビン213、チヌビン234、チヌビン326、チヌビン327、チヌビン328、チヌビン329、チヌビン571(以上、BASF製)が挙げられる。
本実施形態に係る硬化性組成物には、必要に応じて生成する硬化物の引張特性を調整する物性調整剤を添加しても良い。物性調整剤としては特に限定されないが、例えば、フェノキシトリメチルシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、n-プロピルトリメトキシシラン等のアルキルアルコキシシラン類;ジフェニルジメトキシシラン、フェニルトリメトキシシランなどのアリールアルコキシシラン類;ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシラン、γ-グリシドキシプロピルメチルジイソプロペノキシシラン等のアルキルイソプロペノキシシラン;トリス(トリメチルシリル)ボレート、トリス(トリエチルシリル)ボレートなどのトリアルキルシリルボレート類;シリコーンワニス類;ポリシロキサン類等が挙げられる。前記物性調整剤を用いることにより、本実施形態に係る硬化性組成物を硬化させた時の硬度を上げたり、逆に硬度を下げ、破断伸びを出したりし得る。上記物性調整剤は単独で用いてもよく、2種以上併用してもよい。
本実施形態に係る硬化性組成物には、基材への接着性や密着性を高める目的、あるいはその他必要に応じて粘着付与樹脂を添加できる。粘着付与樹脂としては、特に制限はなく通常使用されているものを使うことが出来る。
本実施形態に係る硬化性組成物においてはエポキシ基を含有する化合物を使用できる。エポキシ基を有する化合物を使用すると硬化物の復元性を高めることができる。エポキシ基を有する化合物としてはエポキシ化不飽和油脂類、エポキシ化不飽和脂肪酸エステル類、脂環族エポキシ化合物類、エピクロルヒドリン誘導体に示す化合物及びそれらの混合物等が例示できる。具体的には、エポキシ化大豆油、エポキシ化あまに油、ビス(2-エチルヘキシル)-4,5-エポキシシクロヘキサン-1,2-ジカーボキシレート(E-PS)、エポキシオクチルステアレート、エポキシブチルステアレート等が挙げられる。エポキシ化合物は、(メタ)アクリル酸エステル系共重合体(A)100重量部に対して0.5~50重量部の範囲で使用するのがよい。
本実施形態に係る硬化性組成物には光硬化性物質を使用できる。光硬化性物資を使用すると硬化物表面に光硬化性物質の皮膜が形成され、硬化物のべたつきや硬化物の耐候性を改善できる。この種の化合物には有機単量体、オリゴマー、樹脂或いはそれらを含む組成物等多くのものが知られており、代表的なものとしては、アクリル系又はメタクリル系不飽和基を1ないし数個有するモノマー、オリゴマー或いはそれ等の混合物である不飽和アクリル系化合物、ポリケイ皮酸ビニル類あるいはアジド化樹脂等が使用できる。
本実施形態に係る硬化性組成物には酸素硬化性物質を使用することができる。酸素硬化性物質には空気中の酸素と反応し得る不飽和化合物を例示でき、空気中の酸素と反応して硬化物の表面付近に硬化皮膜を形成し表面のべたつきや硬化物表面へのゴミやホコリの付着を防止するなどの作用をする。酸素硬化性物質の具体例には、キリ油、アマニ油などで代表される乾性油や、該化合物を変性して得られる各種アルキッド樹脂;乾性油により変性されたアクリル系重合体、エポキシ系樹脂、シリコン樹脂;ブタジエン、クロロプレン、イソプレン、1,3-ペンタジエンなどのジエン系化合物を重合または共重合させて得られる1,2-ポリブタジエン、1,4-ポリブタジエン、C5~C8ジエンの重合体などの液状重合体などが挙げられる。これらは単独で用いてもよく、2種以上併用してもよい。
本実施形態に係る硬化性組成物にはエポキシ樹脂を併用することができる。エポキシ樹脂を添加した組成物は特に接着剤、殊に外壁タイル用接着剤として好ましい。エポキシ樹脂としてはビスフェノールA型エポキシ樹脂類またはノボラック型エポキシ樹脂などが挙げられる。
実施例中の数平均分子量及び重量平均分子量は、以下の条件で測定したGPC分子量である。
送液システム:東ソー製HLC-8220GPC
カラム:東ソー製TSK-GEL Hタイプ
溶媒:THF
分子量:ポリスチレン換算
測定温度:40℃
硫黄原子濃度は、(メタ)アクリル酸エステル系共重合体(A)の製造に使用した単量体成分の合計量と、メルカプト基を有する連鎖移動剤(a3)の量から算出した理論値である。
数平均分子量が約4,020(末端基換算分子量2,980)のポリオキシプロピレングリコールに、U-360(ジブチル錫ビス(イソオクチルメルカプトプロピオネート 日東化成(株))60ppmを添加し、ポリオキシプロピレングリコールの水酸基に対してカレンズAOI(2-イソシアナートエチルアクリレート 昭和電工(株))0.93当量を滴下し、5.5%の酸素を含んだ窒素雰囲気中で、80℃で1時間反応を行い、両末端にアクリロイル基を有し(即ち、重合体1分子中に約2個のアクリロイル基を有し)、数平均分子量が4,020、重量平均分子量が4,860であるポリオキシアルキレン系重合体(a2-1)を得た。
数平均分子量が約4,020(末端基換算分子量2,980)のポリオキシプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキサイドの重合を行い、両末端に水酸基を有し、数平均分子量21,100(末端基換算分子量13,600)、分子量分布Mw/Mn=1.21のポリオキシプロピレンを得た。得られたポリオキシプロピレンにU-360を60ppm添加し、ポリオキシプロピレンの水酸基に対してカレンズAOIを0.93当量滴下し、5.5%の酸素を含んだ窒素雰囲気中で、80℃で1時間反応を行い、両末端にアクリロイル基を有し(即ち、重合体1分子中に約2個のアクリロイル基を有し)、数平均分子量が21,100、重量平均分子量が24,930であるポリオキシアルキレン系重合体(a2-2)を得た。
数平均分子量が約4,020(末端基換算分子量2,980)のポリオキシプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキサイドの重合を行い、両末端に水酸基を有し、数平均分子量28,340(末端基換算分子量17,700)、分子量分布Mw/Mn=1.24のポリオキシプロピレンを得た。得られたポリオキシプロピレンにU-360を60ppm添加し、ポリオキシプロピレンの水酸基に対してカレンズAOIを0.93当量滴下し、5.5%の酸素を含んだ窒素雰囲気中で、80℃で1時間反応を行い、両末端にアクリロイル基を有し(即ち、重合体1分子中に約2個のアクリロイル基を有し)、数平均分子量が28,340、重量平均分子量が35,170であるポリオキシアルキレン系重合体(a2-3)を得た。
数平均分子量が約4,020(末端基換算分子量2,980)のポリオキシプロピレングリコールに、該ポリオキシプロピレングリコールの水酸基に対して1.2モル当量のナトリウムメトキシドを28%メタノール溶液として添加した。真空脱揮によりメタノールを留去した後、ポリオキシプロピレングリコールの水酸基に対して1.79モル当量の塩化アリルを添加して末端の水酸基をアリル基に変換した。得られた未精製のアリル基末端ポリオキシプロピレン100重量部に対し、n-ヘキサン300重量部と、水300重量部を混合攪拌した後、遠心分離により水を除去した後、得られたヘキサン溶液に更に水300重量部を混合攪拌し、再度遠心分離により水を除去した後、ヘキサンを減圧脱揮により除去した。以上により、末端にアリル基を有し、数平均分子量が4,020、重量平均分子量が4,860であるポリオキシアルキレン系重合体(p-1)を得た。
攪拌機を備えた四口フラスコにイソブタノール41.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート59.7重量部、ステアリルメタクリレート10.1重量部、合成例1で作製した多官能性マクロモノマー(a2-1)21.9重量部、3-メタクリロキシプロピルトリメトキシシラン1.0重量部、3-メルカプトプロピルトリメトキシシラン7.3重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.7重量部をイソブタノール8.1重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が2,470(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-1)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.070mmol/g、反応性ケイ素基当量は0.42mmol/gであり、硫黄原子濃度は10,941ppmである。
攪拌機を備えた四口フラスコにイソブタノール78.4重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート41.0重量部、ステアリルメタクリレート7.0重量部、合成例1で作製した多官能性マクロモノマー(a2-1)44.4.重量部、3-メタクリロキシプロピルトリメトキシシラン0.7重量部、3-メルカプトプロピルトリメトキシシラン6.9重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.7重量部をイソブタノール8.1重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が3,000(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-2)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.12mmol/g、反応性ケイ素基当量は0.34mmol/gであり、硫黄原子濃度は10,291ppmである。
攪拌機を備えた四口フラスコにイソブタノール58.9重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート47.4重量部、ステアリルメタクリレート8.0重量部、合成例1で作製した多官能性マクロモノマー(a2-1)33.3重量部、3-メタクリロキシプロピルトリメトキシシラン0.8重量部、3-メルカプトプロピルトリメトキシシラン10.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.7重量部をイソブタノール8.1重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が1,910(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-3)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.094mmol/g、反応性ケイ素基当量は0.53mmol/gであり、硫黄原子濃度は15,961ppmである。
攪拌機を備えた四口フラスコにイソブタノール46.4重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート46.0重量部、ブチルアクリレート11.2重量部、ステアリルメタクリレート7.6重量部、合成例2で作製した多官能性マクロモノマー(a2-2)32.9重量部、3-メタクリロキシプロピルトリメトキシシラン1.0重量部、3-メルカプトプロピルトリメトキシシラン1.3重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール10.7重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール8.5重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が7,410(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-4)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.016mmol/g、反応性ケイ素基当量は0.11mmol/gであり、硫黄原子濃度は2,149ppmである。
攪拌機を備えた四口フラスコにイソブタノール44.0重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート51.4重量部、ブチルアクリレート12.5重量部、ステアリルメタクリレート8.5重量部、合成例2で作製した多官能性マクロモノマー(a2-2)25.0重量部、3-メタクリロキシプロピルトリメトキシシラン1.1重量部、3-メルカプトプロピルトリメトキシシラン1.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.4重量部をイソブタノール11.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール9.5重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が8,120(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-5)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.012mmol/g、反応性ケイ素基当量は0.12mmol/gであり、硫黄原子濃度は2,402ppmである。
攪拌機を備えた四口フラスコにイソブタノール44.0重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート51.5重量部、ブチルアクリレート13.5重量部、ステアリルメタクリレート8.5重量部、合成例2で作製した多官能性マクロモノマー(a2-2)25.0重量部、3-メルカプトプロピルトリメトキシシラン1.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.4重量部をイソブタノール11.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール9.5重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が7,930(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-6)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.012mmol/g、反応性ケイ素基当量は0.075mmol/gであり、硫黄原子濃度は2,401ppmである。
攪拌機を備えた四口フラスコにイソブタノール44.2重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート50.9重量部、ブチルアクリレート12.3重量部、ステアリルメタクリレート8.4重量部、合成例2で作製した多官能性マクロモノマー(a2-2)24.7重量部、3-メタクリロキシプロピルトリメトキシシラン2.2重量部、n-ドデシルメルカプタン1.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.4重量部をイソブタノール11.8重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール9.4重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が7,610(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-7)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.012mmol/g、反応性ケイ素基当量は0.088mmol/gであり、硫黄原子濃度は2,417ppmである。
攪拌機を備えた四口フラスコにSOLVESSO100(安藤パラケミー株式会社製)25.6重量部、及び、ミネラルスピリット(大伸化学株式会社製)25.6重量部を入れ、窒素雰囲気下、110℃まで昇温した。そこに、メチルメタクリレート55.1重量部、ブチルアクリレート8.8重量部、ステアリルメタクリレート8.1重量部、合成例3で作製した多官能性マクロモノマー(a2-3)25.0重量部、3-メタクリロキシプロピルトリメトキシシラン1.5重量部、3-メルカプトプロピルトリメトキシシラン1.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.4重量部をSOLVESSO100 8.8重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.2重量部をSOLVESSO100 5.3重量部に溶解した混合溶液を加え110℃で2時間重合を行い、数平均分子量が4,860(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-8)の溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.0092mmol/g、反応性ケイ素基当量は0.14mmol/gであり、硫黄原子濃度は2,396ppmである。
攪拌機を備えた四口フラスコにSOLVESSO100(安藤パラケミー株式会社製) 25.6重量部、及び、ミネラルスピリット(大伸化学株式会社製)25.6重量部を入れ、窒素雰囲気下、110℃まで昇温した。そこに、メチルメタクリレート54.6重量部、ブチルアクリレート8.7重量部、ステアリルメタクリレート8.0重量部、合成例3で作製した多官能性マクロモノマー(a2-3)24.8重量部、3-メタクリロキシプロピルトリメトキシシラン1.5重量部、3-メルカプトプロピルトリメトキシシラン2.4重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.4重量部をSOLVESSO100 8.8重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.2重量部をSOLVESSO100 5.3重量部に溶解した混合溶液を加え110℃で2時間重合を行い、数平均分子量が5,360(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(A-9)の溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.0091mmol/g、反応性ケイ素基当量は0.18mmol/gであり、硫黄原子濃度は3,912ppmである。
攪拌機を備えた四口フラスコにイソブタノール36.9重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート63.1重量部、ステアリルメタクリレート12.6重量部、合成例1で作製した多官能性マクロモノマー(a2-1)23.1重量部、3-メタクリロキシプロピルトリメトキシシラン1.2重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。反応中にゲル化が起こり、ポリマー溶液を得ることができなかった。なお、この合成例14を、表1では比較例1として示した。
攪拌機を備えた四口フラスコにイソブタノール38.1重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート87.4重量部、ステアリルメタクリレート9.8重量部、3-メタクリロキシプロピルトリメトキシシラン1.0重量部、3-メルカプトプロピルトリメトキシシラン1.8重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.7重量部をイソブタノール8.1重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が3,730(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(P-2)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の反応性ケイ素基当量は0.13mmol/gであり、硫黄原子濃度は2,939ppmである。
攪拌機を備えた四口フラスコにイソブタノール41.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、ブチルアクリレート49.7重量部、ステアリルメタクリレート10.0重量部、合成例4で作製したアリル末端ポリオキシアルキレン系重合体(p-1)23.1重量部、3-メタクリロキシプロピルトリメトキシシラン10.0重量部、3-メルカプトプロピルトリメトキシシラン7.2重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)1.8重量部をイソブタノール20.9重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.7重量部をイソブタノール8.1重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が1,980(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(P-3)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の反応性ケイ素基当量は0.72mmol/gであり、硫黄原子濃度は10,948ppmである。
攪拌機を備えた四口フラスコにイソブタノール48.0重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート42.4重量部、ブチルアクリレート10.3重量部、ステアリルメタクリレート7.0重量部、合成例2で作製した多官能性マクロモノマー(a2-2)30.3重量部、3-メタクリロキシプロピルトリメトキシシラン0.9重量部、3-メルカプトプロピルトリメトキシシラン9.1重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール9.8重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.2重量部をイソブタノール7.9重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が1,830(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(P-4)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.014mmol/g、反応性ケイ素基当量は0.50mmol/gであり、硫黄原子濃度は14,846ppmである。
攪拌機を備えた四口フラスコにイソブタノール49.1重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート40.1重量部、ブチルアクリレート9.7重量部、ステアリルメタクリレート6.6重量部、合成例2で作製した多官能性マクロモノマー(a2-2)28.7重量部、3-メタクリロキシプロピルトリメトキシシラン6.3重量部、3-メルカプトプロピルトリメトキシシラン8.6重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.3重量部をイソブタノール9.3重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.2重量部をイソブタノール7.4重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が1,920(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(P-5)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の多官能性マクロモノマー当量は0.014mmol/g、反応性ケイ素基当量は0.69mmol/gであり、硫黄原子濃度は14,037ppmである。
攪拌機を備えた四口フラスコにイソブタノール44.4重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート40.8重量部、ブチルアクリレート54.2重量部、2-エチルヘキシルアクリレート0.5重量部、ステアリルメタクリレート0.5重量部、3-メタクリロキシプロピルトリメトキシシラン0.5重量部、3-メルカプトプロピルトリメトキシシラン3.5重量部、及び2,2’-アゾビス(2-メチルブチロニトリル)0.5重量部をイソブタノール15.6重量部に溶解した混合溶液を5時間かけて滴下した。さらに2,2’-アゾビス(2-メチルブチロニトリル)0.1重量部をイソブタノール4.7重量部に溶解した混合溶液を加え105℃で2時間重合を行い、数平均分子量が3,770(GPC分子量)である反応性ケイ素基含有(メタ)アクリル酸エステル系共重合体(P-6)のイソブタノール溶液(固形分60%)を得た。当該溶液の固形分の反応性ケイ素基当量は0.20mmol/gであり、硫黄原子濃度は5,716ppmである。
合成例5~7で得られた(メタ)アクリル酸エステル系共重合体(A-1)~(A-3)のイソブタノール溶液、及び、合成例15~16で得られた(メタ)アクリル酸エステル系共重合体(P-2)~(P-3)のイソブタノール溶液から、イソブタノールを加熱脱揮し、得られた各重合体の粘度を以下の方法によって測定した。
治具として直径25mmのコーンプレート(2°)を用い、ギャップを60μmに設定し、回転速度が0.1sec-1の時の各重合体の粘度を測定した。装置はTAインスツルメンツ製レオメーター(ARES-G2)を使用した。得られた結果を表1に示す。
(2)ステアリルメタクリレート
(3)3-メタクリロキシプロピルトリメトキシシラン
(4)3-メルカプトプロピルトリメトキシシラン
合成例8~11で得られた(メタ)アクリル酸エステル系共重合体(A-4)~(A-7)のイソブタノール溶液、又は、合成例17~19で得られた(メタ)アクリル酸エステル系共重合体(P-4)~(P-6)のイソブタノール溶液を用い、硬化させて得た硬化物の引張り物性を以下の方法によって測定した。
各重合体溶液に、硬化触媒としてネオスタンU-20(ジブチル錫ジブチルマレート 日東化成(株)製)1重量部(各重合体溶液の固形分100重量部に対する量)を混合し、厚さ100μmのシートを作製した。得られたシートを23℃50%RH条件下で2週間硬化養生を行った。得られたシートから70mm×10mmの短冊試験片を切り出し、掴み具間距離を40mmに設定し、23℃で引張り物性を測定した。30%伸長時応力(M30)、破断時の強度(TB)、破断時の伸び(EB)、及び、ヤング率を測定した。引張り物性は(株)島津製オートグラフ(AGS-X)を用い20mm/minの引張り速度で測定を行った。得られた結果を表2に示す。
(2)n-ブチルアクリレート
(3)2-エチルヘキシルアクリレート
(4)ステアリルメタクリレート
(5)3-メタクリロキシプロピルトリメトキシシラン
(6)3-メルカプトプロピルトリメトキシシラン
(7)n-ドデシルメルカプタン
多官能性マクロモノマー(a2)を使用せずに合成した比較例6の(メタ)アクリル酸エステル系共重合体(P-6)からは、硬化物が柔らかすぎて、試験片を作製できなかった。
合成例12~13で得られた(メタ)アクリル酸エステル系共重合体(A-8)~(A-9)の芳香族炭化水素系溶剤と脂肪族炭化水素系溶剤の混合溶液を用い、硬化させて得た硬化物の引張り物性を上述した方法によって測定した。
(2)n-ブチルアクリレート
(4)ステアリルメタクリレート
(5)3-メタクリロキシプロピルトリメトキシシラン
(6)3-メルカプトプロピルトリメトキシシラン
Claims (15)
- 下記式(1)に示す反応性ケイ素基を有する(メタ)アクリル酸エステル系共重合体(A)であって、
該共重合体を構成する単量体成分が、
(メタ)アクリル酸エステル(a1)、
(メタ)アクリロイル基を分子内に1つより多く有するポリオキシアルキレン系重合体(a2)、及び、
メルカプト基を有する連鎖移動剤(a3)、を含有し、
ポリオキシアルキレン系重合体(a2)/メルカプト基を有する連鎖移動剤(a3)のモル比が、0.06以上であり、並びに
前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体(a4)をさらに含有し、及び/又は、メルカプト基を有する連鎖移動剤(a3)が、反応性ケイ素基をさらに有する、(メタ)アクリル酸エステル系共重合体(A)。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。) - 式:(共重合体(A)の重量平均分子量)/(ポリオキシアルキレン系重合体(a2)の重量平均分子量)で算出される値が、0.65以上である、請求項1に記載の(メタ)アクリル酸エステル系共重合体(A)。
- ポリオキシアルキレン系重合体(a2)が、前記単量体成分中0.08モル%以上6.0モル%以下を占める、請求項1又は2に記載の(メタ)アクリル酸エステル系共重合体(A)。
- メルカプト基を有する連鎖移動剤(a3)が、前記単量体成分中0.4モル%以上15モル%以下を占める、請求項1~3のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- ポリオキシアルキレン系重合体(a2)の数平均分子量が50,000以下である、請求項1~4のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- ポリオキシアルキレン系重合体(a2)の含有量が、前記単量体成分中60重量%以下である、請求項1~5のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- 共重合体(A)の分子量分布が3.0以上11.0以下である、請求項1~6のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- 前記式(1)におけるcが0である、請求項1~7のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- (メタ)アクリル酸エステル(a1)は、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも1種の単量体を含有する、請求項1~8のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- ポリオキシアルキレン系重合体(a2)を除く前記単量体成分の総量のうち、(メタ)アクリル酸エステル(a1)成分である、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも1種の単量体が占める割合が60重量%以上である、請求項9に記載の(メタ)アクリル酸エステル系共重合体(A)。
- (メタ)アクリル酸エステル系共重合体(A)中の硫黄原子濃度が700ppm以上20,000ppm以下である、請求項1~10のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)。
- 下記式(1)に示す反応性ケイ素を有する(メタ)アクリル酸エステル系共重合体(A)であって、
前記共重合体は、2つの第一分子鎖が、1つの第二分子鎖を介して結合している構造を含み、第二分子鎖の両末端がそれぞれ、第一分子鎖の非末端部位に結合しており、
第一分子鎖は(メタ)アクリル酸エステル系重合体の分子鎖から構成され、
第二分子鎖はポリオキシアルキレン系重合体の分子鎖から構成され、
前記反応性ケイ素基は、第一分子鎖に結合し、
第一分子鎖は、いずれかの末端に、-S-R3(式中、Sは硫黄原子を表し、R3は、前記反応性ケイ素基を有していてもよい炭化水素基を表す)で表される構造を有し、
前記-S-R3に対する前記ポリオキシアルキレン系重合体のモル比が、0.06以上である、(メタ)アクリル酸エステル系共重合体(A)。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。) - 請求項1~12のいずれか1項に記載の(メタ)アクリル酸エステル系共重合体(A)を含む硬化性組成物。
- 請求項13に記載の硬化性組成物の硬化物。
- 下記式(1)に示す反応性ケイ素基を有する(メタ)アクリル酸エステル系共重合体(A)の製造方法であって、
単量体成分を共重合する工程を含み、
前記単量体成分が、
(メタ)アクリル酸エステル(a1)、
(メタ)アクリロイル基を分子内に1つより多く有するポリオキシアルキレン系重合体(a2)、及び、
メルカプト基を有する連鎖移動剤(a3)、を含有し、
ポリオキシアルキレン系重合体(a2)/メルカプト基を有する連鎖移動剤(a3)のモル比が、0.06以上であり、並びに
前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体(a4)をさらに含有し、及び/又は、メルカプト基を有する連鎖移動剤(a3)が、反応性ケイ素基をさらに有する、(メタ)アクリル酸エステル系共重合体(A)の製造方法。
-SiR1 cX3-c (1)
(式中、R1は、置換又は非置換の炭素数1~20の炭化水素基を表す。Xは水酸基または加水分解性基を表す。cは0または1である。)
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JPS5273998A (en) | 1975-12-16 | 1977-06-21 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing compositions |
JPS5978222A (ja) * | 1982-10-26 | 1984-05-07 | Sunstar Giken Kk | 室温硬化性弾性組成物 |
JPS59122541A (ja) | 1982-12-28 | 1984-07-16 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JPH03160053A (ja) | 1989-11-16 | 1991-07-10 | Kanegafuchi Chem Ind Co Ltd | 室温硬化性組成物 |
JPH04283259A (ja) | 1991-03-11 | 1992-10-08 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JPH09194731A (ja) | 1996-01-23 | 1997-07-29 | Asahi Glass Co Ltd | 硬化性組成物 |
JP2008045059A (ja) * | 2006-08-18 | 2008-02-28 | Asahi Glass Co Ltd | 硬化性組成物 |
JP5082851B2 (ja) | 2005-08-25 | 2012-11-28 | 東亞合成株式会社 | 硬化性樹脂組成物 |
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2022
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JPS5273998A (en) | 1975-12-16 | 1977-06-21 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing compositions |
JPS5978222A (ja) * | 1982-10-26 | 1984-05-07 | Sunstar Giken Kk | 室温硬化性弾性組成物 |
JPS59122541A (ja) | 1982-12-28 | 1984-07-16 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JPH03160053A (ja) | 1989-11-16 | 1991-07-10 | Kanegafuchi Chem Ind Co Ltd | 室温硬化性組成物 |
JPH04283259A (ja) | 1991-03-11 | 1992-10-08 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
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JP5082851B2 (ja) | 2005-08-25 | 2012-11-28 | 東亞合成株式会社 | 硬化性樹脂組成物 |
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US20200157266A1 (en) * | 2018-11-20 | 2020-05-21 | Dentsply Sirona Inc. | Compositions and methods to antibacterial nanogel and hydrolytically stable antibacterial nanogel for dental compositions |
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