JP2014196409A - Active energy ray-curable aqueous resin composition, active energy ray-curable aqueous coating, article applied with the coating - Google Patents
Active energy ray-curable aqueous resin composition, active energy ray-curable aqueous coating, article applied with the coating Download PDFInfo
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- JP2014196409A JP2014196409A JP2013072529A JP2013072529A JP2014196409A JP 2014196409 A JP2014196409 A JP 2014196409A JP 2013072529 A JP2013072529 A JP 2013072529A JP 2013072529 A JP2013072529 A JP 2013072529A JP 2014196409 A JP2014196409 A JP 2014196409A
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- Prior art keywords
- active energy
- energy ray
- meth
- resin composition
- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 119
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 64
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 29
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 26
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000003973 paint Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000101 thioether group Chemical group 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 28
- 238000003860 storage Methods 0.000 abstract description 24
- 239000000758 substrate Substances 0.000 abstract description 14
- -1 polyoxyethylene group Polymers 0.000 description 61
- 229920000642 polymer Polymers 0.000 description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 43
- 239000004793 Polystyrene Substances 0.000 description 33
- 229920002223 polystyrene Polymers 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- 239000003999 initiator Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 16
- 239000012965 benzophenone Substances 0.000 description 16
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 15
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- NXMOWTFIUDDXIT-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dioctyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCC(C)(C)C NXMOWTFIUDDXIT-UHFFFAOYSA-L 0.000 description 13
- 239000000374 eutectic mixture Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
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- 238000011156 evaluation Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000005341 toughened glass Substances 0.000 description 6
- 102100026735 Coagulation factor VIII Human genes 0.000 description 5
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001748 polybutylene Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 3
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- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000007689 inspection Methods 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- VJZNUICECYWOFV-UHFFFAOYSA-N o-phenyl carbamothioate Chemical compound NC(=S)OC1=CC=CC=C1 VJZNUICECYWOFV-UHFFFAOYSA-N 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000000913 palmityl 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])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
- 244000144985 peep Species 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000007363 ring formation reaction Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 239000006120 scratch resistant coating Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([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
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YYBMRDFADFQHGU-UHFFFAOYSA-N tert-butyl (2-methylpropan-2-yl)oxy carbonate Chemical class CC(C)(C)OOC(=O)OC(C)(C)C YYBMRDFADFQHGU-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-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
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- VJMQFIRIMMSSRW-UHFFFAOYSA-N trimethyl(phenylsulfanyl)silane Chemical compound C[Si](C)(C)SC1=CC=CC=C1 VJMQFIRIMMSSRW-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られる活性エネルギー線硬化型水性樹脂組成物、該組成物を含有する活性エネルギー線硬化型水性塗料、及び該塗料で塗装された物品に関する。 The present invention relates to an active energy ray-curable aqueous resin composition that is excellent in storage stability and provides a high-hardness coating film having high adhesion to a glass substrate, and an active energy ray-curable aqueous paint containing the composition And articles coated with the paint.
活性エネルギー線硬化型組成物は、塗装基材への熱履歴が少なく、塗膜硬度や擦り傷性に優れるという特長から、家電製品、携帯電話等のプラスチック基材用ハードコート剤として使用されてきた。このような活性エネルギー線硬化型組成物としては、例えば、アクリルアクリレート等の重合性不飽和二重結合を有するポリマーや重合性アクリル樹脂等の不飽和二重結合を有さないポリマーと、重合性単量体と、希釈剤として有機溶剤とを含有する活性エネルギー線硬化型組成物(溶剤型の活性エネルギー線硬化型組成物)が挙げられる。この活性エネルギー線硬化型組成物を、例えば、スプレー塗装用塗料として用いる場合、前記有機溶剤を該塗料中に50〜90質量%と多量に含有させる必要がある。そのため、該樹脂組成物を含有する活性エネルギー線硬化型塗料を用いてプラスチック等の基材表面に硬化塗膜を形成させる際に該塗料中の有機溶剤が揮発する事で作業環境を悪化させる問題があった。また、この揮発した有機溶剤は大気汚染の原因にもなっていた。 The active energy ray-curable composition has been used as a hard coating agent for plastic substrates for home appliances, mobile phones, etc. because it has a low heat history on the coating substrate and excellent coating film hardness and scratch resistance. . Examples of such an active energy ray-curable composition include a polymer having a polymerizable unsaturated double bond such as acrylic acrylate and a polymer having no unsaturated double bond such as a polymerizable acrylic resin, and a polymerizable property. Examples include an active energy ray-curable composition (solvent-type active energy ray-curable composition) containing a monomer and an organic solvent as a diluent. When this active energy ray-curable composition is used as, for example, a paint for spray coating, the organic solvent needs to be contained in a large amount of 50 to 90% by mass in the paint. Therefore, the problem of worsening the working environment due to volatilization of the organic solvent in the paint when forming a cured coating film on the surface of a substrate such as plastic using the active energy ray-curable paint containing the resin composition was there. The volatilized organic solvent has also caused air pollution.
これに対して、希釈剤として有機溶剤ではなく水を用いる活性エネルギー線硬化型水性樹脂組成物が提案されている(例えば、特許文献1及び2参照。)。この活性エネルギー線硬化型水性樹脂組成物では、樹脂へ導入したカルボキシル基等の酸基をアンモニアや有機アミンで中和することにより、樹脂の水への溶解性や分散性を確保しているが、被塗装物がガラス基材の場合、硬化塗膜の密着性が低く、剥がれやすいという問題があった。 On the other hand, an active energy ray-curable aqueous resin composition using water instead of an organic solvent as a diluent has been proposed (see, for example, Patent Documents 1 and 2). In this active energy ray-curable aqueous resin composition, acid groups such as carboxyl groups introduced into the resin are neutralized with ammonia or organic amines to ensure the solubility and dispersibility of the resin in water. When the object to be coated is a glass substrate, there is a problem that the adhesiveness of the cured coating film is low and it is easy to peel off.
そこで、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られる活性エネルギー線硬化型水性樹脂組成物が求められていた。 Therefore, there has been a demand for an active energy ray-curable aqueous resin composition that is excellent in storage stability and can provide a high-hardness coating film having high adhesion to a glass substrate.
本発明が解決しようとする課題は、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られる活性エネルギー線硬化型水性樹脂組成物、該組成物を含有する活性エネルギー線硬化型水性塗料、及び該塗料で塗装された物品を提供することである。 The problem to be solved by the present invention is an active energy ray-curable aqueous resin composition that provides a high-hardness coating film having excellent storage stability and high adhesion to a glass substrate, and activity containing the composition It is to provide an energy ray curable water-based paint and an article coated with the paint.
本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、特定のアクリル樹脂と、ポリイソシアネート化合物と、水酸基を有する(メタ)アクリレートとの反応物を含有する樹脂組成物と、アルコキシシリル基を有する化合物とを含有する混合物を、水媒体中で分散させることで得られる活性エネルギー線硬化型水性樹脂組成物は、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition containing a reaction product of a specific acrylic resin, a polyisocyanate compound, and a (meth) acrylate having a hydroxyl group, and an alkoxy The active energy ray-curable aqueous resin composition obtained by dispersing a mixture containing a compound having a silyl group in an aqueous medium has excellent storage stability and high adhesion to a glass substrate. The present inventors have found that a hardness coating film can be obtained and completed the present invention.
すなわち、本発明は、ポリオキシアルキレン基を有するアクリル単量体(a1)、水酸基を有するアクリル単量体(a2)、並びに前記アクリル単量体(a1)及びアクリル単量体(a2)以外のアクリル単量体(a3)を必須原料として共重合して得られたアクリル樹脂(A)と、ポリイソシアネート化合物(B)と、水酸基を有する(メタ)アクリレート(C)との反応物を含有する樹脂組成物(X)と、アルコキシシリル基を有する化合物(Y)とを含有する混合物を、水媒体中で分散させることで得られることを特徴とする活性エネルギー線硬化型水性樹脂組成物、該組成物を含有する活性エネルギー線硬化型水性塗料、及び該塗料で塗装された物品に関する。 That is, the present invention provides an acrylic monomer (a1) having a polyoxyalkylene group, an acrylic monomer (a2) having a hydroxyl group, and other than the acrylic monomer (a1) and the acrylic monomer (a2). Contains a reaction product of an acrylic resin (A) obtained by copolymerization using an acrylic monomer (a3) as an essential raw material, a polyisocyanate compound (B), and a (meth) acrylate (C) having a hydroxyl group. An active energy ray-curable aqueous resin composition obtained by dispersing a mixture containing a resin composition (X) and a compound (Y) having an alkoxysilyl group in an aqueous medium, The present invention relates to an active energy ray-curable water-based paint containing a composition, and an article coated with the paint.
本発明の活性エネルギー線硬化型水性樹脂組成物は、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られることから、活性エネルギー線硬化型水性塗料に有用であり、該塗料を各種物品に塗装することができる。したがって、本発明の活性エネルギー線硬化型水性樹脂組成物は、棚類の扉、ガラス棚板、水槽等に多用されるフロートガラス、高層ビルの外装に用いられる倍強化ガラス、複写機用原稿台、スキャナー、航空機用風防、電子レンジ用ドア、タッチパネル、電磁調理器に用いられる化学強化ガラス、化学工業用プラントののぞき窓、照明機器、顕微鏡用スライドガラス、半導体、太陽電池、防弾ガラス等に用いられる耐熱ガラス、防火区画壁、避難通路、避難階段間仕切りに用いられる低膨張防火ガラス、耐火遮熱積層ガラス、網無し耐熱強化ガラス、超耐熱結晶化ガラス等の飛散防止コーティング剤、耐擦傷コーティング剤、防汚コーティング剤等に好適に用いることができる。 The active energy ray-curable aqueous resin composition of the present invention is useful for active energy ray-curable aqueous coatings because it has excellent storage stability and provides a high-hardness coating film having high adhesion to a glass substrate. Yes, the paint can be applied to various articles. Accordingly, the active energy ray-curable aqueous resin composition of the present invention includes float glass frequently used for doors of shelves, glass shelves, water tanks, double tempered glass used for the exterior of high-rise buildings, and a document table for copying machines. Used in scanners, aircraft windshields, microwave oven doors, touch panels, chemically tempered glass used in electromagnetic cookers, chemical industrial plant peep windows, lighting equipment, microscope slides, semiconductors, solar cells, bulletproof glass, etc. Heat-resistant glass, fire-proof compartment walls, evacuation passages, low-expansion fire-proof glass used for partitioning evacuation stairs, fire-resistant and heat-insulated laminated glass, netless heat-resistant tempered glass, super-heat-resistant crystallized glass, anti-scattering coating agent, scratch-resistant coating agent It can be suitably used for an antifouling coating agent or the like.
本発明の活性エネルギー線硬化型水性樹脂組成物は、ポリオキシアルキレン基を有するアクリル単量体(a1)、水酸基を有するアクリル単量体(a2)、並びに前記アクリル単量体(a1)及びアクリル単量体(a2)以外のアクリル単量体(a3)を必須原料として共重合して得られたアクリル樹脂(A)と、ポリイソシアネート化合物(B)と、水酸基を有する(メタ)アクリレート(C)との反応物を含有する樹脂組成物(X)と、アルコキシシリル基を有する化合物(Y)とを含有する混合物を、水媒体中で分散させることで得られるものである。 The active energy ray-curable aqueous resin composition of the present invention includes an acrylic monomer (a1) having a polyoxyalkylene group, an acrylic monomer (a2) having a hydroxyl group, and the acrylic monomer (a1) and acrylic. Acrylic resin (A) obtained by copolymerizing acrylic monomer (a3) other than monomer (a2) as an essential raw material, polyisocyanate compound (B), and (meth) acrylate (C) having a hydroxyl group ) And a mixture containing a resin composition (X) containing a reaction product with an alkoxysilyl group (Y) is dispersed in an aqueous medium.
まず、前記樹脂組成物(X)について説明する。この樹脂組成物(X)は、前記アクリル樹脂(A)と、前記ポリイソシアネート化合物(B)と、前記水酸基を有する(メタ)アクリレート(C)との反応物を含有するものである。 First, the resin composition (X) will be described. This resin composition (X) contains a reaction product of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C) having a hydroxyl group.
前記アクリル樹脂(A)は、その原料として、ポリオキシアルキレン基を有するアクリル単量体(a1)、水酸基を有するアクリル単量体(a2)、並びに前記アクリル単量体(a1)及びアクリル単量体(a2)以外のアクリル単量体(a3)を必須原料として共重合したものである。 The acrylic resin (A) includes, as raw materials, an acrylic monomer (a1) having a polyoxyalkylene group, an acrylic monomer (a2) having a hydroxyl group, and the acrylic monomer (a1) and an acrylic monomer. A copolymer obtained by copolymerizing an acrylic monomer (a3) other than the body (a2) as an essential raw material.
前記アクリル単量体(a1)は、ポリオキシアルキレン基及び(メタ)アクリロイル基を有する化合物である。前記ポリオキシアルキレン基としては、例えば、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基等が挙げられる。 The acrylic monomer (a1) is a compound having a polyoxyalkylene group and a (meth) acryloyl group. Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and the like.
なお、本発明において、「(メタ)アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいい、「(メタ)アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「(メタ)アクリロイル基」とは、メタクリロイル基とアクリロイル基の一方又は両方をいう。 In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meta) The “) acryloyl group” means one or both of a methacryloyl group and an acryloyl group.
また、前記アクリル単量体(a1)としては、例えば、下記一般式(1)で表されるものが挙げられる。 Moreover, as said acrylic monomer (a1), what is represented by following General formula (1) is mentioned, for example.
上記一般式(1)中のX、Y及びZはアルキレン基であるが、このアルキレン基としては、エチレン基、プロピレン基、ブチレン基等が挙げられ、これらのアルキレン基には、置換基を有しているものも含まれる。 X, Y and Z in the general formula (1) are alkylene groups, and examples of the alkylene group include an ethylene group, a propylene group and a butylene group. These alkylene groups have a substituent. The thing which is doing is also included.
上記一般式(1)中のp、q及びrは、オキシアルキレンの繰り返し単位数を表すが、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、その合計が4〜100のものが好ましく、6〜50のものがより好ましく、8〜25のものがさらに好ましい。なお、Xを含む繰り返し単位、Yを含む繰り返し単位及びZを含む繰り返し単位は、ランダム状に配置されてもブロック状に配置されても構わない。 P, q, and r in the general formula (1) represent the number of repeating units of oxyalkylene, but the dispersibility in water is improved, and the storage stability of the resulting active energy ray-curable aqueous resin composition is improved. In order to improve, the thing of 4-100 is preferable, the thing of 6-50 is more preferable, and the thing of 8-25 is further more preferable. In addition, the repeating unit containing X, the repeating unit containing Y, and the repeating unit containing Z may be arrange | positioned at random or a block shape.
上記一般式(1)中のR2は、水素原子、炭素原子数1〜6のアルキル基又はフェニル基である。R2が水素の場合は、前記アクリル単量体(a1)は、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリアルキレングリコールのモノ(メタ)アクリル酸エステルとなり、R2が炭素原子数1〜6のアルキル基又はフェニル基の場合は、アルキレングリコールのモノ(メタ)アクリル酸エステルの(メタ)アクリロイル基ではない末端が炭素原子数1〜6のアルキル基又はフェニル基によって封止されたものとなる。これらの中でも、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、R2が炭素原子数1〜3のアルキル基のものが好ましく、R2がメチル基のものがより好ましい。 R 2 in the general formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. When R 2 is hydrogen, the acrylic monomer (a1) is a mono (meth) acrylic acid ester of a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., and R 2 has 1 to 1 carbon atoms. In the case of an alkyl group of 6 or a phenyl group, a terminal that is not a (meth) acryloyl group of a mono (meth) acrylic ester of alkylene glycol is sealed with an alkyl group or phenyl group having 1 to 6 carbon atoms Become. Among these, R 2 is preferably an alkyl group having 1 to 3 carbon atoms because dispersibility in water is improved and the storage stability of the resulting active energy ray-curable aqueous resin composition is improved. R 2 is more preferably a methyl group.
前記アクリル単量体(a1)のより具体的な例としては、ポリエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレート、プロポキシポリエチレングリコール(メタ)アクリレート、ブトキシポリエチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、エトキシポリプロピレングリコール(メタ)アクリレート、プロポキシポリプロピレングリコール(メタ)アクリレート、ブトキシポリプロピレングリコール(メタ)アクリレート、フェノキシポリプロピレングリコール(メタ)アクリレート、ポリブチレングリコール(メタ)アクリレート、メトキシポリブチレングリコール(メタ)アクリレート、エトキシポリブチレングリコール(メタ)アクリレート、プロポキシポリブチレングリコール(メタ)アクリレート、ブトキシポリブチレングリコール(メタ)アクリレート、フェノキシポリブチレングリコール(メタ)アクリレート、ポリエチレングリコール−ポリプロピレングリコール(メタ)アクリレート、メトキシポリエチレングリコール−ポリプロピレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール−ポリプロピレングリコール(メタ)アクリレート、ポリエチレングリコール−ポリブチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール−ポリブチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール−ポリブチレングリコール(メタ)アクリレート等が挙げられる。これらのアクリル単量体(a1)の中でも、前記アクリル樹脂(A)の水媒体への分散性が良好になることから、ポリオキシエチレン基を有するものが好ましい。また、これらのアクリル単量体(a1)は、単独で用いることも2種以上併用することもできる。 More specific examples of the acrylic monomer (a1) include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, and butoxypolyethylene. Glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate, butoxypolypropylene glycol (meta ) Acrylate, phenoxy polypropylene glycol (meth) Chlorate, polybutylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate, propoxypolybutylene glycol (meth) acrylate, butoxypolybutylene glycol (meth) acrylate, phenoxypolybutylene glycol (Meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, methoxypolyethylene glycol-polypropylene glycol (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene Glycol-polybutylenegri Lumpur (meth) acrylate, phenoxy polyethylene glycol - polybutylene glycol (meth) acrylate. Among these acrylic monomers (a1), those having a polyoxyethylene group are preferable because the dispersibility of the acrylic resin (A) in an aqueous medium is improved. Moreover, these acrylic monomers (a1) can be used alone or in combination of two or more.
前記アクリル単量体(a2)は、水酸基及び(メタ)アクリロイル基を有する化合物である。このアクリル単量体(a2)の具体例としては、2−ヒドロキシエチル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシ−n−ブチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシ−n−ブチル(メタ)アクリレート、3−ヒドロキシ−n−ブチル(メタ)アクリレート、1,4−シクロヘキサンジメタノールモノ(メタ)アクリレート、N−(2−ヒドロキシエチル)(メタ)アクリルアミド、グリセリンモノ(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリレート、2−(メタ)アクリロイルオキシエチル−2−ヒドロキシエチルフタレート、末端に水酸基を有するラクトン変性(メタ)アクリレート等が挙げられる。なお、これらのアクリル単量体(a2)は、単独で用いることも2種以上併用することもできる。 The acrylic monomer (a2) is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the acrylic monomer (a2) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) ) Acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2- Mud carboxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal. These acrylic monomers (a2) can be used alone or in combination of two or more.
また、前記アクリル単量体(a3)は、前記アクリル単量体(a1)及び(a2)以外のアクリル単量体であるが、例えば、(メタ)アクリル酸、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、n−ペンチル(メタ)アクリレート、n−ヘキシル(メタ)アクリレート、n−ヘプチル(メタ)アクリレート、n−オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、セチル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、4−tert−ブチルシクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ベンジル(メタ)アクリレート、アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、(メタ)アクリロニトリル、N,N−ジメチルアミノエチル(メタ)アクリレート、グリシジル(メタ)アクリレート;3−(メタ)アクリロキシプロピルトリメトキシシラン等が挙げられる。これらのアクリル単量体(a3)の中でも、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性がより向上することから、脂肪族又は脂環式アクリル単量体が好ましく、この中でも、脂環式アクリル単量体がより好ましい。また、これらのアクリル単量体(a3)は、単独で用いることも2種以上併用することもできる。 The acrylic monomer (a3) is an acrylic monomer other than the acrylic monomers (a1) and (a2). For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n- Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) Acrylate, behenyl (meth) acrylate , Cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N, N-dimethyl (meth) Examples include acrylamide, (meth) acrylonitrile, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate; 3- (meth) acryloxypropyltrimethoxysilane. Among these acrylic monomers (a3), since the storage stability of the obtained active energy ray-curable aqueous resin composition is further improved, an aliphatic or alicyclic acrylic monomer is preferable, and among these, An alicyclic acrylic monomer is more preferable. Moreover, these acrylic monomers (a3) can be used alone or in combination of two or more.
さらに、アクリル樹脂(A)の原料として、上記の必須原料であるアクリル単量体(a1)、アクリル単量体(a2)、及びアクリル単量体(a3)以外のその他の単量体(a4)を用いても構わない。このその他の単量体(a4)としては、スチレン、α−メチルスチレン、p−メチルスチレン、p−メトキシスチレン等の芳香族ビニル単量体などが挙げられる。 Furthermore, as a raw material of the acrylic resin (A), the other essential monomers (a4) other than the acrylic monomer (a1), the acrylic monomer (a2), and the acrylic monomer (a3) which are the essential raw materials described above. ) May be used. Examples of the other monomer (a4) include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.
前記アクリル単量体(a1)の使用量は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、前記アクリル樹脂(A)の原料である単量体成分中の20〜90質量%の範囲が好ましく、30〜80質量%の範囲がより好ましく、40〜70質量%の範囲がさらに好ましい。また、前記アクリル単量体(a2)の使用量は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、前記アクリル樹脂(A)の原料である単量体成分中の2〜30質量%の範囲が好ましく、3〜25質量%の範囲がより好ましく、5〜20質量%の範囲がさらに好ましい。なお、前記アクリル単量体(a3)、必要に応じて用いるその他の単量体(a4)の使用量は、前記アクリル樹脂(A)の原料である単量体成分の合計100質量%から上記のアクリル単量体(a1)及びアクリル単量体(a2)の使用比率を除いた残部となるが、前記アクリル単量体(a3)として、3−(メタ)アクリロキシプロピルトリメトキシシラン等のアルコキシシリル基を有する化合物を使用する場合の使用量は、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、前記アクリル樹脂(A)の原料である単量体成分中の2質量%以下であることが好ましい。 The use amount of the acrylic monomer (a1) improves dispersibility in water and improves the storage stability of the resulting active energy ray-curable aqueous resin composition. The range of 20-90 mass% in the monomer component which is a raw material is preferable, the range of 30-80 mass% is more preferable, and the range of 40-70 mass% is further more preferable. Moreover, since the dispersibility in water improves and the storage stability of the obtained active energy ray hardening-type aqueous resin composition improves, the usage-amount of the said acrylic monomer (a2) improves the said acrylic resin (A The range of 2 to 30% by mass in the monomer component which is a raw material of (2) is preferable, the range of 3 to 25% by mass is more preferable, and the range of 5 to 20% by mass is more preferable. In addition, the usage-amount of the said acrylic monomer (a3) and the other monomer (a4) used as needed is the above from the total 100 mass% of the monomer component which is a raw material of the said acrylic resin (A). The acrylic monomer (a1) and the acrylic monomer (a2) are used as the balance except for the ratio of the acrylic monomer (a2). As the acrylic monomer (a3), 3- (meth) acryloxypropyltrimethoxysilane or the like can be used. When the compound having an alkoxysilyl group is used, the amount of the monomer component which is a raw material of the acrylic resin (A) is improved because the storage stability of the obtained active energy ray-curable aqueous resin composition is improved. The content is preferably 2% by mass or less.
前記アクリル樹脂(A)の製造方法としては、前記アクリル単量体(a1)〜(a3)、及び必要に応じて用いるその他の単量体(a4)を、有機溶剤中、重合開始剤を使用して共重合させる方法が挙げられる。ここで用いる有機溶媒としては、アルコール化合物、ケトン化合物、エステル化合物、エーテル化合物、アミド化合物、スルホキシド化合物、炭化水素化合物が好ましく、具体的には、メタノール、エタノール、プロパノール、n−ブタノール、iso−ブタノール、tert−ブタノール、3−メトキシブタノール、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、ジイソプロピルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン、トルエン、キシレン等が挙げられる。これらの中でも、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル等のジアルキレングリコールジアルキルエーテルがより好ましい。 As a manufacturing method of the said acrylic resin (A), the said acrylic monomers (a1)-(a3) and the other monomer (a4) used as needed are used for a polymerization initiator in an organic solvent. And a copolymerization method. The organic solvent used here is preferably an alcohol compound, a ketone compound, an ester compound, an ether compound, an amide compound, a sulfoxide compound, or a hydrocarbon compound, specifically, methanol, ethanol, propanol, n-butanol, or iso-butanol. , Tert-butanol, 3-methoxybutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol di Chill ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide , Tetrahydrofuran, dioxane, toluene, xylene and the like. Among these, dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether are more preferable because the storage stability of the obtained active energy ray-curable aqueous resin composition is improved.
前記重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、3,3,5−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド等のケトンパーオキサイド化合物;1,1−ビス(tert−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(tert−ブチルパーオキシ)シクロヘキサン、n−ブチル−4,4−ビス(tert−ブチルパーオキシ)バレレート、2,2−ビス(4,4−ジtert−ブチルパーオキシシクロヘキシル)プロパン、2,2−ビス(4,4−ジtert−アミルパーオキシシクロヘキシル)プロパン、2,2−ビス(4,4−ジtert−ヘキシルパーオキシシクロヘキシル)プロパン、2,2−ビス(4,4−ジtert−オクチルパーオキシシクロヘキシル)プロパン、2,2−ビス(4,4−ジクミルパーオキシシクロヘキシル)プロパン等のパーオキシケタール化合物;クメンハイドロパーオキサイド、2,5−ジメチルヘキサン−2,5−ジハイドロパーオキサイド等のハイドロパーオキサイド類;1,3−ビス(tert−ブチルパーオキシ−m−イソプロピル)ベンゼン、2,5−ジメチル−2,5−ジ(tert−ブチルパーオキシ)ヘキサン、ジイソプロピルベンゼンパーオキサイド、tert−ブチルクミルパーオキサイド等のジアルキルパーオキサイド化合物;デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド化合物;ビス(tert−ブチルシクロヘキシル)パーオキシジカーボネート等のパーオキシカーボネート化合物;tert−ブチルパーオキシ−2−エチルヘキサノエート、tert−ブチルパーオキシベンゾエート、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン等のパーオキシエステル化合物などの有機過酸化物と、2,2’−アゾビスイソブチロニトリル、1,1’−アゾビス(シクロヘキサン−1−カルボニトリル)等のアゾ化合物とが挙げられる。 Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-bis (4,4-ditert-octylpa Peroxyketal compounds such as oxycyclohexyl) propane and 2,2-bis (4,4-dicumylperoxycyclohexyl) propane; cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, etc. Hydroperoxides: 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert Dialkyl peroxide compounds such as butyl cumyl peroxide; diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; bis (tert-butyl) Peroxycarbonate compounds such as cyclohexyl) peroxydicarbonate; tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane And organic peroxides such as peroxyester compounds, and azo compounds such as 2,2′-azobisisobutyronitrile and 1,1′-azobis (cyclohexane-1-carbonitrile).
また、前記アクリル樹脂(A)を製造する際に、必要に応じて、ラウリルメルカプタン、2−メルカプトエタノ−ル、チオグリセロール、エチルチオグリコ−ル酸、オクチルチオグリコ−ル酸等の連鎖移動剤を使用しても構わない。 Further, when the acrylic resin (A) is produced, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like is used as necessary. May be used.
前記アクリル樹脂(A)の水酸基価は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、5〜130の範囲が好ましく、10〜100の範囲がより好ましく、15〜80の範囲がさらに好ましい。 The hydroxyl value of the acrylic resin (A) is preferably in the range of 5 to 130, since the dispersibility in water is improved and the storage stability of the resulting active energy ray-curable aqueous resin composition is improved. The range of -100 is more preferable, and the range of 15-80 is more preferable.
前記アクリル樹脂(A)の重量平均分子量(Mw)は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、3,000〜100,000の範囲が好ましく、4,000〜50,000の範囲がより好ましく、5,000〜30,000の範囲がさらに好ましい。ここで、重量平均分子量(Mw)はゲル浸透クロマトグラフィー(以下、「GPC」と略記する。)測定に基づきポリスチレン換算した値である。なお、GPCの測定条件は以下の通りである。 The acrylic resin (A) has a weight average molecular weight (Mw) of 3,000 to 100 because the dispersibility in water is improved and the storage stability of the resulting active energy ray-curable aqueous resin composition is improved. , Preferably in the range of 4,000 to 50,000, more preferably in the range of 5,000 to 30,000. Here, the weight average molecular weight (Mw) is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.
[GPC測定条件]
測定装置:高速GPC装置(東ソー株式会社製「HLC−8220GPC」)
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度4mg/mLのテトラヒドロフラン溶液)
標準試料:下記の単分散ポリスチレンを用いて検量線を作成した。
[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
(単分散ポリスチレン)
東ソー株式会社製「TSKgel 標準ポリスチレン A−500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A−2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F−1」
東ソー株式会社製「TSKgel 標準ポリスチレン F−2」
東ソー株式会社製「TSKgel 標準ポリスチレン F−4」
東ソー株式会社製「TSKgel 標準ポリスチレン F−10」
東ソー株式会社製「TSKgel 標準ポリスチレン F−20」
東ソー株式会社製「TSKgel 標準ポリスチレン F−40」
東ソー株式会社製「TSKgel 標準ポリスチレン F−80」
東ソー株式会社製「TSKgel 標準ポリスチレン F−128」
東ソー株式会社製「TSKgel 標準ポリスチレン F−288」
東ソー株式会社製「TSKgel 標準ポリスチレン F−550」
(Monodispersed polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
前記ポリイソシアネート化合物(B)について説明する。このポリイソシアネート化合物(B)としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、m−キシリレンジイソシアネート、m−フェニレンビス(ジメチルメチレン)ジイソシアネート等の芳香族ジイソシアネート化合物;ヘキサメチレンジイソシアネート、リジンジイソシアネート、1,3−ビス(イソシアナトメチル)シクロヘキサン、2−メチル−1,3−ジイソシアナトシクロヘキサン、2−メチル−1,5−ジイソシアナトシクロヘキサン、4,4’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート等の脂肪族又は脂環式ジイソシアネート化合物などが挙げられる。これらの中でも、耐黄変性に優れることから、脂肪族又は脂環式ジイソシアネート化合物が好ましい。 The polyisocyanate compound (B) will be described. Examples of the polyisocyanate compound (B) include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylenebis (dimethylmethylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1, Fats such as 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate And an aliphatic or alicyclic diisocyanate compound. Among these, an aliphatic or alicyclic diisocyanate compound is preferable because of excellent yellowing resistance.
また、前記ポリイソシアネート化合物(B)として、上記のジイソシアネート化合物を多価アルコールと付加反応させて得られるイソシアネート基を有するプレポリマー;上記のジイソシアネート化合物を環化三量化させて得られるイソシアヌレート環を有する化合物;上記のジイソシアネート化合物を水と反応させて得られる尿素結合やビュレット結合を有するポリイソシアネート化合物;2−イソシアナトエチル(メタ)アクリレート、3−イソプロペニル−α,α−ジメチルベンジルイソシアネート、(メタ)アクリロイルイソシアネート等のイソシアネート基を有するアクリル単量体の単独重合体;前記イソシアネート基を有するアクリル単量体と、その他のアクリル単量体、ビニルエステル化合物、ビニルエーテル化合物、芳香族ビニル単量体、フルオロオレフィン等の単量体と共重合することによって得られるイソシアネート基を有する共重合体なども用いることができる。 Further, as the polyisocyanate compound (B), a prepolymer having an isocyanate group obtained by addition reaction of the diisocyanate compound with a polyhydric alcohol; an isocyanurate ring obtained by cyclization and trimerization of the diisocyanate compound. A compound having urea bond or burette bond obtained by reacting the above diisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, ( A homopolymer of an acrylic monomer having an isocyanate group such as (meth) acryloyl isocyanate; the acrylic monomer having an isocyanate group and other acrylic monomers, a vinyl ester compound, a vinyl ether compound, an aromatic vinyl A copolymer having an isocyanate group obtained by copolymerization with a monomer such as an nyl monomer or fluoroolefin can also be used.
上記のポリイソシアネート化合物(B)は、単独で用いることも2種以上併用することもできる。 Said polyisocyanate compound (B) can be used individually or can be used together 2 or more types.
前記(メタ)アクリレート(C)について説明する。この(メタ)アクリレート(C)は、水酸基及び重合性不飽和基として(メタ)アクリロイル基を有する化合物である。この(メタ)アクリレート(C)としては、例えば、2−ヒドロキシエチル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシ−n−ブチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシ−n−ブチル(メタ)アクリレート、3−ヒドロキシ−n−ブチル(メタ)アクリレート、1,4−シクロヘキサンジメタノールモノ(メタ)アクリレート、N−(2−ヒドロキシエチル)(メタ)アクリルアミド、グリセリンモノ(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリレート、2−(メタ)アクリロイルオキシエチル−2−ヒドロキシエチルフタレート、末端に水酸基を有するラクトン変性(メタ)アクリレート等の水酸基を有する単官能(メタ)アクリレート;トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート等の水酸基を有する多官能(メタ)アクリレートなどが挙げられる。これらの(メタ)アクリレート(C)は、単独で用いることも2種以上併用することもできる。 The (meth) acrylate (C) will be described. This (meth) acrylate (C) is a compound having a (meth) acryloyl group as a hydroxyl group and a polymerizable unsaturated group. Examples of the (meth) acrylate (C) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, and 2-hydroxypropyl (meth). Acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) Acrylamide, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl- -Hydroxyethyl phthalate, monofunctional (meth) acrylate having a hydroxyl group such as lactone-modified (meth) acrylate having a hydroxyl group at the terminal; trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Examples include polyfunctional (meth) acrylates having a hydroxyl group such as (meth) acrylate. These (meth) acrylates (C) can be used alone or in combination of two or more.
前記(メタ)アクリレート(C)の中でも、低粘度のため取り扱いが容易で、得られた活性エネルギー線硬化型水性樹脂組成物から得られる硬化塗膜の表面硬度を高くできることから、ペンタエリスリトールトリアクリレートが好ましい。 Among the (meth) acrylates (C), since it is easy to handle because of its low viscosity, and the surface hardness of the cured coating film obtained from the obtained active energy ray-curable aqueous resin composition can be increased, pentaerythritol triacrylate Is preferred.
前記樹脂組成物(X)は、前記アクリル樹脂(A)と、前記ポリイソシアネート化合物(B)と、前記水酸基を有する(メタ)アクリレート(C)との反応物を含有するものであるが、前記アクリル樹脂(A)、前記ポリイソシアネート化合物(B)、前記水酸基を有する(メタ)アクリレート(C)の反応方法としては、例えば、前記アクリル樹脂(A)、ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)を同時に反応させる方法、前記ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)を反応させた後、前記アクリル樹脂(A)を反応させる方法、前記アクリル樹脂(A)及びポリイソシアネート化合物(B)を反応させた後、前記(メタ)アクリレート(C)を反応させる方法等が挙げられるが、いずれの方法でも構わない。 The resin composition (X) contains a reaction product of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C) having a hydroxyl group. Examples of the reaction method of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C) having a hydroxyl group include, for example, the acrylic resin (A), the polyisocyanate compound (B), and (meth). A method of reacting acrylate (C) simultaneously, a method of reacting the polyisocyanate compound (B) and (meth) acrylate (C) and then reacting the acrylic resin (A), the acrylic resin (A) and poly Examples include a method of reacting the (meth) acrylate (C) after reacting the isocyanate compound (B). It may be in the way.
前記アクリル樹脂(A)、ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)の反応は、無触媒でも行うことはできるが、反応の進行を促進させるため、ウレタン化触媒の存在下で行うことが好ましい。前記ウレタン化触媒としては、例えば、ピリジン、ピロール、トリエチルアミン、ジエチルアミン、ジブチルアミン等のアミン化合物;トリフェニルホスフィン、トリエチルホスフィン等のホフィン化合物;ジブチル錫ジラウレート、オクチル錫トリラウレート、オクチル錫ジアセテート、ジブチル錫ジアセテート、オクチル酸錫等の有機錫化合物、オクチル酸亜鉛等の有機金属化合物などが挙げられる。これらのウレタン化触媒の中でも、ジブチル錫ジラウレートが好ましい。 The reaction of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C) can be performed without a catalyst, but is performed in the presence of a urethanization catalyst in order to promote the progress of the reaction. It is preferable. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphine compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organotin compounds such as diacetate and tin octylate, and organometallic compounds such as zinc octylate. Among these urethanization catalysts, dibutyltin dilaurate is preferable.
前記アクリル樹脂(A)と前記(メタ)アクリレート(C)との質量比[(A)/(C)]は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、0.2〜8.0の範囲が好ましく、0.3〜4.5の範囲がより好ましく、0.5〜2.5の範囲がさらに好ましい。 The mass ratio [(A) / (C)] of the acrylic resin (A) and the (meth) acrylate (C) is improved in dispersibility in water, and the resulting active energy ray-curable aqueous resin composition is obtained. Therefore, the range of 0.2 to 8.0 is preferable, the range of 0.3 to 4.5 is more preferable, and the range of 0.5 to 2.5 is more preferable.
また、前記アクリル樹脂(A)、ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)の使用量は、水中での分散性が向上し、得られる活性エネルギー線硬化型水性樹脂組成物の貯蔵安定性が向上することから、前記ポリイソシアネート化合物(B)が有するイソシアネート基のモル数1に対して、前記アクリル樹脂(A)が有する水酸基及び前記(メタ)アクリレート(C)が有する水酸基の合計モル数が、0.2〜1.2となる範囲が好ましく、0.4〜1.0となる範囲がより好ましい。 Moreover, the usage-amount of the said acrylic resin (A), a polyisocyanate compound (B), and (meth) acrylate (C) improves the dispersibility in water, and storage of the obtained active energy ray hardening-type aqueous resin composition. Since the stability is improved, the total number of hydroxyl groups of the acrylic resin (A) and hydroxyl groups of the (meth) acrylate (C) with respect to the number of moles of isocyanate groups of the polyisocyanate compound (B) is 1. The range in which the number of moles is 0.2 to 1.2 is preferable, and the range in which 0.4 to 1.0 is more preferable.
また、前記アクリル樹脂(A)、ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)の反応の際に、有機溶剤が存在する場合、ポリイソシアネート化合物(B)と反応する有機溶剤は、脱溶剤しておくことが好ましい。 In the reaction of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C), when an organic solvent is present, the organic solvent that reacts with the polyisocyanate compound (B) is removed. It is preferable to use a solvent.
前記樹脂組成物(X)は、上記のアクリル樹脂(A)、ポリイソシアネート化合物(B)及び(メタ)アクリレート(C)の反応物以外に、多官能(メタ)アクリレート(D)を含有しても構わない。この多官能(メタ)アクリレート(D)としては、例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,3−ブタンジオールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ(メタ)アクリレート、ビスフェノールA−ジ(メタ)アクリレート、ビスフェノールA−EO変性ジ(メタ)アクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸EO変性トリアクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンEO変性トリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等が挙げられる。 The resin composition (X) contains a polyfunctional (meth) acrylate (D) in addition to the reaction product of the acrylic resin (A), the polyisocyanate compound (B), and the (meth) acrylate (C). It doesn't matter. As this polyfunctional (meth) acrylate (D), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) a Relate, bisphenol A-di (meth) acrylate, bisphenol A-EO modified di (meth) acrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified Examples include tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate, and the like.
次に、前記アルコキシシリル基を有する化合物(Y)について説明する。前記アルコキシシリル基を有する化合物(Y)としては、例えば、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン等のアミノ基とアルコキシシリル基とを有するアミノシラン化合物;3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピル(ジメトキシ)メチルシラン、3−(2,8,9−トリオキサ−5−アザ−1−シラビシクロ[3.3.3]ウンデカ−1−イル)−1−プロパンチオール、等のメルカプト基とアルコキシシリル基とを有するメルカプトシラン化合物;ビス(トリエトキシシリルプロピル)テトラスルフィド、(フェニルチオ)トリメチルシラン、エチレンジチオビス(トリメトキシシラン)、ビス[3−(トリエトキシシリル)プロピル]テトラスルフィド、3−((2−(2,8,9−トリオキサ−5−アザ−1−シラビシクロ(3.3.3)ウンデカ−1−イル)エチル)チオ)プロパンニトリル、ビス[3−(2,8,9−トリオキサ−5−アザ−1−シラビシクロ[3.3.3]ウンデカ−1−イル)プロピル]ジスルフィド、S−[2−(2,8,9−トリオキサ−5−アザ−1−シラビシクロ(3.3.3)ウンデカ−1−イル)エチル]フェニルチオカルバメート、等のスルフィド基とアルコキシシリル基を有するスルフィドシラン化合物;2−(3、4−エポキシシクロヘキシル)エチルトリメトキシシラン、2−(3、4−エポキシシクロヘキシル)エチルトリエトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン等のエポキシ基とアルコキシシリル基とを有するエポキシシラン化合物;3−(メタ)アクリロキシプロピルトリメトキシシラン、p−スチリルトリメトキシシラン、ビニルトリメトキシシラン、3−クロロプロピルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ−n−ブトキシシラン、エチルトリメトキシシラン、n−プロピルトリメトキシシラン、iso−ブチルトリメトキシシラン、シクロヘキシルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジ−n−ブトキシシラン、ジエチルジメトキシシラン、ジフェニルジメトキシシラン、メチルシクロヘキシルジメトキシシラン、メチルフェニルジメトキシシラン等が挙げられる。なお、これらのアルコキシシリル基を有する化合物(Y)は、単独で用いることも2種以上併用することもできる。 Next, the compound (Y) having the alkoxysilyl group will be described. Examples of the compound (Y) having an alkoxysilyl group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N- An aminosilane compound having an amino group and an alkoxysilyl group such as 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- (2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undec-1-yl) -1-propanethiol, etc. A device having a mercapto group and an alkoxysilyl group. Captosilane compound; bis (triethoxysilylpropyl) tetrasulfide, (phenylthio) trimethylsilane, ethylenedithiobis (trimethoxysilane), bis [3- (triethoxysilyl) propyl] tetrasulfide, 3-((2- (2 , 8,9-Trioxa-5-aza-1-silabicyclo (3.3.3) undec-1-yl) ethyl) thio) propanenitrile, bis [3- (2,8,9-trioxa-5-aza -1-silabicyclo [3.3.3] undec-1-yl) propyl] disulfide, S- [2- (2,8,9-trioxa-5-aza-1-silabicyclo (3.3.3) undeca -1-yl) ethyl] phenylthiocarbamate, sulfide silane compounds having a sulfide group and an alkoxysilyl group; 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Epoxysilane compounds having an epoxy group and an alkoxysilyl group such as propylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane; 3- (meth) acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, vinyl Trimethoxysilane, 3-chloropropyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, Chlorotrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane, methylphenyldimethoxysilane, etc. Is mentioned. In addition, these compounds (Y) having an alkoxysilyl group can be used alone or in combination of two or more.
上記のアルコキシシリル基を有する化合物(Y)の中でも、得られる塗膜のガラス密着性が向上することから、アミノ基とアルコキシシリル基とを有するアミノシラン化合物、メルカプト基とアルコキシシリル基とを有するメルカプトシラン化合物、スルフィド基とアルコキシシリル基を有するスルフィドシラン化合物が好ましい。 Among the compounds (Y) having an alkoxysilyl group, an aminosilane compound having an amino group and an alkoxysilyl group, a mercapto group having a mercapto group and an alkoxysilyl group, because the glass adhesion of the obtained coating film is improved. A silane compound and a sulfide silane compound having a sulfide group and an alkoxysilyl group are preferred.
本発明の活性エネルギー線硬化型水性樹脂組成物は、前記樹脂組成物(X)と、前記アルコキシシリル基を有する化合物(Y)とを含有する混合物を、水媒体中で分散させることで得られるが、貯蔵安定性及び得られる硬化塗膜のガラス基材との密着性が優れることから、前記樹脂組成物(X)の固形分と、前記アルコキシシリル基を有する化合物(Y)との質量比[(X)/(Y)]は、99/1〜80/20の範囲が好ましく、96/4〜91/9の範囲がより好ましい。 The active energy ray-curable aqueous resin composition of the present invention is obtained by dispersing a mixture containing the resin composition (X) and the compound (Y) having an alkoxysilyl group in an aqueous medium. However, since the storage stability and the adhesion of the resulting cured coating film to the glass substrate are excellent, the mass ratio of the solid content of the resin composition (X) and the compound (Y) having the alkoxysilyl group [(X) / (Y)] is preferably in the range of 99/1 to 80/20, and more preferably in the range of 96/4 to 91/9.
前記樹脂組成物(X)と、前記アルコキシシリル基を有する化合物(Y)とを含有する混合物を水媒体中で分散させる方法としては、特に限定されないが、例えば、前記混合物に水を添加する方法、水中に前記混合物を添加する方法等が挙げられる。 A method of dispersing the mixture containing the resin composition (X) and the compound (Y) having an alkoxysilyl group in an aqueous medium is not particularly limited. For example, a method of adding water to the mixture And a method of adding the mixture to water.
本発明の活性エネルギー線硬化型水性樹脂組成物は、貯蔵安定性に優れ、ガラス基材との高い密着性を有する高硬度塗膜が得られることから、活性エネルギー線硬化型水性塗料に好適に用いることができる。 The active energy ray-curable aqueous resin composition of the present invention is suitable for active energy ray-curable aqueous coatings because it has excellent storage stability and a high-hardness coating film having high adhesion to a glass substrate. Can be used.
上記の活性エネルギー線硬化型水性塗料は、本発明の活性エネルギー線硬化型水性樹脂組成物を含有するものであるが、その他の配合物として、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、顔料分散剤等の添加剤を使用することができる。 The above active energy ray-curable water-based paint contains the active energy ray-curable aqueous resin composition of the present invention, but as other formulations, an antistatic agent, an antifoaming agent, a viscosity modifier, light resistance Additives such as a stabilizer, a weather resistance stabilizer, a heat resistance stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, and a pigment dispersant can be used.
また、本発明の活性エネルギー線硬化型水性塗料は、基材に塗布後、活性エネルギー線を照射することで硬化塗膜とすることができる。この活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等の電離放射線をいう。活性エネルギー線として紫外線を照射して硬化塗膜とする場合には、本発明の活性エネルギー線硬化型水性塗料中に光重合開始剤(E)を添加し、硬化性を向上することが好ましい。また、必要であればさらに光増感剤を添加して、硬化性を向上することもできる。一方、電子線、α線、β線、γ線のような電離放射線を用いる場合には、光重合開始剤や光増感剤を用いなくても速やかに硬化するので、特に光重合開始剤(E)や光増感剤を添加する必要はない。 Moreover, the active energy ray-curable aqueous coating material of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case of forming a cured coating film by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator (E) to the active energy ray-curable aqueous coating material of the present invention to improve curability. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. It is not necessary to add E) or a photosensitizer.
前記光重合開始剤(E)としては、分子内開裂型光重合開始剤及び水素引き抜き型光重合開始剤が挙げられる。分子内開裂型光重合開始剤としては、例えば、ジエトキシアセトフェノン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、ベンジルジメチルケタール、1−(4−イソプロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、4−(2−ヒドロキシエトキシ)フェニル−(2−ヒドロキシ−2−プロピル)ケトン、1−ヒドロキシシクロヘキシル−フェニルケトン、2−メチル−2−モルホリノ(4−チオメチルフェニル)プロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン等のアセトフェノン系化合物;ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類;2,4,6−トリメチルベンゾインジフェニルホスフィンオキシド、ビス(2,4,6−トリメチルベンゾイル)−フェニルホスフィンオキシド等のアシルホスフィンオキシド系化合物;ベンジル、メチルフェニルグリオキシエステル等が挙げられる。 Examples of the photopolymerization initiator (E) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.
一方、水素引き抜き型光重合開始剤としては、例えば、ベンゾフェノン、o−ベンゾイル安息香酸メチル−4−フェニルベンゾフェノン、4,4’−ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、4−ベンゾイル−4’−メチル−ジフェニルサルファイド、アクリル化ベンゾフェノン、3,3’,4,4’−テトラ(t−ブチルペルオキシカルボニル)ベンゾフェノン、3,3’−ジメチル−4−メトキシベンゾフェノン等のベンゾフェノン系化合物;2−イソプロピルチオキサントン、2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、2,4−ジクロロチオキサントン等のチオキサントン系化合物;ミヒラ−ケトン、4,4’−ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物;10−ブチル−2−クロロアクリドン、2−エチルアンスラキノン、9,10−フェナンスレンキノン、カンファーキノン等が挙げられる。これらの光重合開始剤(E)は、単独で用いることも、2種以上を併用することもできる。 On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators (E) can be used alone or in combination of two or more.
また、前記光増感剤としては、例えば、脂肪族アミン、芳香族アミン等のアミン類、o−トリルチオ尿素等の尿素類、ナトリウムジエチルジチオホスフェート、s−ベンジルイソチウロニウム−p−トルエンスルホネート等の硫黄化合物などが挙げられる。 Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. And sulfur compounds.
これらの光重合開始剤及び光増感剤の使用量は、本発明の活性エネルギー線硬化型水性塗料中の不揮発成分100質量部に対し、各々0.05〜20質量部が好ましく、0.5〜10質量%がより好ましい。 The amount of these photopolymerization initiator and photosensitizer used is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable aqueous coating material of the present invention. 10 mass% is more preferable.
また、上記の活性エネルギー線硬化型水性樹脂組成物は、棚類の扉、ガラス棚板、水槽等に多用されるフロートガラス、高層ビルの外装に用いられる倍強化ガラス、複写機用原稿台、スキャナー、航空機用風防、電子レンジ用ドア、タッチパネル、電磁調理器に用いられる化学強化ガラス、化学工業用プラントののぞき窓、照明機器、顕微鏡用スライドガラス、半導体、太陽電池、防弾ガラス等に用いられる耐熱ガラス、防火区画壁、避難通路、避難階段間仕切りに用いられる低膨張防火ガラス、耐火遮熱積層ガラス、網無し耐熱強化ガラス、超耐熱結晶化ガラス等の飛散防止コーティング、耐擦傷コーティング、防汚コーティング剤に好適に用いることができる。 In addition, the active energy ray-curable aqueous resin composition includes float glass frequently used for doors of shelves, glass shelves, water tanks, double tempered glass used for exteriors of high-rise buildings, manuscript tables for copying machines, Used in scanners, windshields for aircraft, doors for microwave ovens, touch panels, chemically tempered glass used in electromagnetic cookers, inspection windows for chemical industrial plants, lighting equipment, glass slides for microscopes, semiconductors, solar cells, bulletproof glass, etc. Low-expansion fireproof glass used in heat-resistant glass, fire-proof partition walls, evacuation passages, evacuation staircase partitions, fire-resistant and heat-insulated laminated glass, netless heat-resistant tempered glass, super-heat-resistant crystallized glass, etc. It can be suitably used for a coating agent.
また、本発明の活性エネルギー線硬化型水性塗料の塗装方法としては、用途により異なるが、例えば、グラビアコーター、ロールコーター、コンマコーター、ナイフコーター、エアナイフコーター、カーテンコーター、キスコーター、シャワーコーター、ホイーラーコーター、スピンコーター、ディッピング、スクリーン印刷、スプレー、アプリケーター、バーコーター等の方法が挙げられる。 The method of applying the active energy ray-curable water-based paint of the present invention varies depending on the application. For example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater , Spin coater, dipping, screen printing, spraying, applicator, bar coater and the like.
本発明の活性エネルギー線硬化型水性塗料を硬化させる活性エネルギー線としては、上記の通り、紫外線、電子線、α線、β線、γ線のような電離放射線であるが、具体的なエネルギー源又は硬化装置としては、例えば、殺菌灯、紫外線用蛍光灯、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧又は高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等を光源とする紫外線、又は走査型、カーテン型電子線加速器による電子線等が挙げられる。 As described above, the active energy rays for curing the active energy ray-curable water-based paint of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Or as a curing device, for example, a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Examples of the electron beam include ultraviolet rays, a scanning type, and a curtain type electron beam accelerator.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。なお、重合体の水酸基価及び酸価は、JIS試験方法K 0070−1992に準拠して測定したものである。また、重合体の重量平均分子量(Mw)は、下記のGPC測定条件で測定したものである。 Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the hydroxyl value and acid value of a polymer are measured based on JIS test method K0070-1992. Moreover, the weight average molecular weight (Mw) of a polymer is measured on the following GPC measurement conditions.
[GPC測定条件]
測定装置:高速GPC装置(東ソー株式会社製「HLC−8220GPC」)
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度4mg/mLのテトラヒドロフラン溶液)
標準試料:下記の単分散ポリスチレンを用いて検量線を作成した。
[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
(単分散ポリスチレン)
東ソー株式会社製「TSKgel 標準ポリスチレン A−500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A−2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F−1」
東ソー株式会社製「TSKgel 標準ポリスチレン F−2」
東ソー株式会社製「TSKgel 標準ポリスチレン F−4」
東ソー株式会社製「TSKgel 標準ポリスチレン F−10」
東ソー株式会社製「TSKgel 標準ポリスチレン F−20」
東ソー株式会社製「TSKgel 標準ポリスチレン F−40」
東ソー株式会社製「TSKgel 標準ポリスチレン F−80」
東ソー株式会社製「TSKgel 標準ポリスチレン F−128」
東ソー株式会社製「TSKgel 標準ポリスチレン F−288」
東ソー株式会社製「TSKgel 標準ポリスチレン F−550」
(Monodispersed polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
〔合成例1:重合体(A−1)の合成〕
攪拌機、温度計、冷却管及び窒素導入管を備えた4つ口のフラスコに、ジエチレングリコールジメチルエーテル292gを仕込み、窒素気流下に110℃に昇温した後、メトキシポリエチレングリコールアクリレート(1分子当たりのオキシエチレン単位数:平均13;以下、「13EOA」と略記する。)322g、2−ヒドロキシエチルメタクリレート(以下、「HEMA」と略記する。)90g、イソボルニルアクリレート(以下、「IBA」と略記する。)232g、t−ブチルパーオキシ−2−エチルヘキサノエート10g、t−ブチルパーオキシベンゾエート3g及びジエチレングリコールジメチルエーテル51gからなる混合液を5時間かけて滴下した。滴下後、110℃で3時間反応して、重量平均分子量が12,000であり、水酸基価が60である重合体(A−1)の溶液(樹脂分65質量%)を得た。
[Synthesis Example 1: Synthesis of polymer (A-1)]
292 g of diethylene glycol dimethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen introduction pipe, heated to 110 ° C. under a nitrogen stream, and then methoxypolyethylene glycol acrylate (oxyethylene per molecule) Number of units: average 13; hereinafter abbreviated as “13EOA”) 322 g, 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”) 90 g, isobornyl acrylate (hereinafter abbreviated as “IBA”). ) A liquid mixture consisting of 232 g, 10 g of t-butylperoxy-2-ethylhexanoate, 3 g of t-butylperoxybenzoate and 51 g of diethylene glycol dimethyl ether was added dropwise over 5 hours. After dripping, it reacted at 110 degreeC for 3 hours, and obtained the solution (resin content 65 mass%) of the polymer (A-1) whose weight average molecular weight is 12,000 and whose hydroxyl value is 60.
〔合成例2:重合体(A−2)の合成〕
攪拌機、温度計、冷却管及び窒素導入管を備えた4つ口のフラスコに、ジエチレングリコールジメチルエーテル292gを仕込み、窒素気流下に110℃に昇温した後、メトキシポリエチレングリコールメタクリレート(1分子当たりのオキシエチレン単位数:平均23;以下、「23EOMA」と略記する。)322g、HEMA90g、IBA232g、t−ブチルパーオキシ−2−エチルヘキサノエート10g、t−ブチルパーオキシベンゾエート3g及びジエチレングリコールジメチルエーテル51gからなる混合液を5時間かけて滴下した。滴下後、110℃で3時間反応して、重量平均分子量が13,000であり、水酸基価が60である重合体(A−2)の溶液(樹脂分65質量%)を得た。
[Synthesis Example 2: Synthesis of Polymer (A-2)]
292 g of diethylene glycol dimethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen introduction pipe, heated to 110 ° C. under a nitrogen stream, and then methoxypolyethylene glycol methacrylate (oxyethylene per molecule). Number of units: average 23; hereinafter abbreviated as “23EOMA”.) Mixture of 322 g, HEMA 90 g, IBA 232 g, t-butyl peroxy-2-ethylhexanoate 10 g, t-butyl peroxybenzoate 3 g and diethylene glycol dimethyl ether 51 g The solution was added dropwise over 5 hours. After dripping, it reacted at 110 degreeC for 3 hours, and obtained the solution (resin content 65 mass%) of the polymer (A-2) whose weight average molecular weight is 13,000 and whose hydroxyl value is 60.
〔合成例3:重合体(A−3)の合成〕
攪拌機、温度計、冷却管及び窒素導入管を備えた4つ口のフラスコに、ジエチレングリコールジメチルエーテル292gを仕込み、窒素気流下に110℃に昇温した後、13EOA322g、HEMA90g、IBA232g、t−ブチルパーオキシ−2−エチルヘキサノエート10g、t−ブチルパーオキシベンゾエート3g及びジエチレングリコールジメチルエーテル51gからなる混合液を5時間かけて滴下した。滴下後、110℃で3時間反応して、重量平均分子量が12,500であり、水酸基価が60である重合体(A−3)の溶液(樹脂分65質量%)を得た。
[Synthesis Example 3: Synthesis of Polymer (A-3)]
292 g of diethylene glycol dimethyl ether was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen introduction pipe, heated to 110 ° C. under a nitrogen stream, then 13 EOA 322 g, HEMA 90 g, IBA 232 g, t-butylperoxy A mixed solution consisting of 10 g of 2-ethylhexanoate, 3 g of t-butyl peroxybenzoate and 51 g of diethylene glycol dimethyl ether was added dropwise over 5 hours. After dripping, it reacted at 110 degreeC for 3 hours, and obtained the solution (resin content 65 mass%) of the polymer (A-3) whose weight average molecular weight is 12,500 and whose hydroxyl value is 60.
〔合成例4:重合体(A−4)の合成〕
攪拌機、温度計、冷却管及び窒素導入管を備えた4つ口のフラスコに、ジエチレングリコールジメチルエーテル298gを仕込み、窒素気流下に110℃に昇温した後、13EOA322g、HEMA75g、IBA231g、アクリル酸(以下、「AA」と略記する。)17g、t−ブチルパーオキシ−2−エチルヘキサノエート10g、t−ブチルパーオキシベンゾエート2g及びジエチレングリコールジメチルエーテル47gからなる混合液を5時間かけて滴下した。滴下後、110℃で3時間反応して、重量平均分子量が11,500であり、水酸基価が50である重合体(A−4)の溶液(樹脂分65質量%)を得た。
[Synthesis Example 4: Synthesis of Polymer (A-4)]
Into a four-necked flask equipped with a stirrer, thermometer, cooling pipe and nitrogen introduction pipe, 298 g of diethylene glycol dimethyl ether was charged and heated to 110 ° C. under a nitrogen stream, then 13 EOA 322 g, HEMA 75 g, IBA 231 g, acrylic acid (hereinafter referred to as Abbreviated as “AA”.) A mixture of 17 g, 10 g of t-butylperoxy-2-ethylhexanoate, 2 g of t-butylperoxybenzoate and 47 g of diethylene glycol dimethyl ether was added dropwise over 5 hours. After dripping, it reacted at 110 degreeC for 3 hours, and obtained the solution (resin content 65 mass%) of the polymer (A-4) whose weight average molecular weight is 11,500 and whose hydroxyl value is 50.
〔合成例5:重合体(RA−1)の合成〕
攪拌機、温度計、冷却管及び窒素導入管を備えた4つ口のフラスコに、ジエチレングリコールジメチルエーテル340g、ω−カルボキシ−ポリカプロラクトンモノアクリレート(東亞合成株式会社製「アロニックス M5300」;以下、「clA」と略記する。)13gを仕込み、窒素気流下に110℃に昇温した後、HEMA39g、メチルメタクリレート(以下、「MMA」と略記する。)390g、n−ブチルアクリレート(以下、「BA」と略記する。)130g、AA78g、及びt−ブチルパーオキシ−2−エチルヘキサノエート9gからなる混合液を5時間かけて滴下した。滴下後、110℃で9時間反応して、重量平均分子量が35,000であり、酸価が97である重合体(RA−1)の溶液(樹脂分65質量%)を得た。
[Synthesis Example 5: Synthesis of polymer (RA-1)]
To a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen introduction pipe, 340 g of diethylene glycol dimethyl ether, ω-carboxy-polycaprolactone monoacrylate (“Aronix M5300” manufactured by Toagosei Co., Ltd .; 13 g is charged and heated to 110 ° C. under a nitrogen stream, and then 39 g of HEMA, 390 g of methyl methacrylate (hereinafter abbreviated as “MMA”), and 390 g of n-butyl acrylate (hereinafter abbreviated as “BA”). .) A mixed solution consisting of 130 g, AA 78 g, and t-butylperoxy-2-ethylhexanoate 9 g was added dropwise over 5 hours. After dripping, it reacted at 110 degreeC for 9 hours, and obtained the solution (resin content 65 mass%) of the polymer (RA-1) whose weight average molecular weight is 35,000 and whose acid value is 97.
〔合成例6:ウレタンアクリレート組成物(RB−1)の合成〕
攪拌機、温度計及び冷却管を備えた4つ口フラスコに、ヘキサメチレンジイソシアネート(以下、「HDI」と略記する。)104g、メトキノン0.2g、及びジブチル錫ジラウレート0.2gを仕込み、撹拌を開始し60℃に昇温した。同温度で、ペンタエリスリトールトリアクリレート(以下、「PETA」と略記する。)及びペンタエリスリトールテトラアクリレートの混合物(東亞合成株式会社製「アロニックス M305」、ペンタエリスリトールトリアクリレート比率:60質量%、水酸基価:115;以下、「PETA混合物」と略記する。)645gを10回に分けて10分毎に仕込んだ。さらに5時間反応を継続して系中のイソシアネート百分率が0.2%以下であることを確認して反応を終了し、ウレタンアクリレートとペンタエリスリトールテトラアクリレートとの混合物であるウレタンアクリレート組成物(RB−1)を得た。
[Synthesis Example 6: Synthesis of urethane acrylate composition (RB-1)]
A four-necked flask equipped with a stirrer, a thermometer and a condenser tube was charged with 104 g of hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 0.2 g of methoquinone, and 0.2 g of dibutyltin dilaurate, and stirring was started. The temperature was raised to 60 ° C. At the same temperature, a mixture of pentaerythritol triacrylate (hereinafter abbreviated as “PETA”) and pentaerythritol tetraacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate ratio: 60 mass%, hydroxyl value: 115; hereinafter abbreviated as “PETA mixture”.) 645 g was charged in 10 portions every 10 minutes. The reaction was further continued for 5 hours to confirm that the isocyanate percentage in the system was 0.2% or less, and the reaction was terminated. A urethane acrylate composition (RB--), which was a mixture of urethane acrylate and pentaerythritol tetraacrylate. 1) was obtained.
なお、上記の合成例1〜5で合成した重合体(A−1)〜(A−4)及び(RA−1)の単量体組成を表1に示す。 In addition, Table 1 shows monomer compositions of the polymers (A-1) to (A-4) and (RA-1) synthesized in Synthesis Examples 1 to 5.
〔実施例1:活性エネルギー線硬化型水性樹脂組成物(W−1)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、4,4’−ジシクロヘキシルメタンジイソシアネート(以下、「H12MDI」と略記する。)69g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物222gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液149g(重合体(A−1)として97g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−アミノプロピルトリエトキシシラン31gを仕込み、30分間撹拌した後、イオン交換水527gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−1)を得た。
[Example 1: Preparation of active energy ray-curable aqueous resin composition (W-1)]
In a four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and an air introduction pipe, 69 g of 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as “H 12 MDI”), 0.1 g of methoquinone, 3, After charging 1.3 g of 5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate and raising the temperature to 50 ° C. under an air stream, 222 g of PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 149 g of a 65% by mass solution of the polymer (A-1) obtained in Synthesis Example 1 (97 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Subsequently, the system temperature was cooled to 30 ° C., 31 g of 3-aminopropyltriethoxysilane was added, and the mixture was stirred for 30 minutes, and then 527 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-1) was obtained.
〔実施例2:活性エネルギー線硬化型水性樹脂組成物(W−2)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI70g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物225gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例2で得られた重合体(A−2)の65質量%溶液151g(重合体(A−2)として98g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン16gを仕込み、30分間撹拌した後、イオン交換水535gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−2)を得た。
[Example 2: Preparation of active energy ray-curable aqueous resin composition (W-2)]
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air inlet tube, 70 g of H 12 MDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate are added. After charging and raising the temperature to 50 ° C. under an air stream, 225 g of the PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 151 g of a 65% by mass solution of the polymer (A-2) obtained in Synthesis Example 2 (98 g as the polymer (A-2)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature is cooled to 30 ° C., 16 g of N-2- (aminoethyl) -3-aminopropyltriethoxysilane is added, and after stirring for 30 minutes, 535 g of ion-exchanged water is added to obtain an aqueous dispersion. It was. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-2) was obtained.
〔実施例3:活性エネルギー線硬化型水性樹脂組成物(W−3)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI71g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物227gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例3で得られた重合体(A−3)の65質量%溶液153g(重合体(A−3)として99g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン8gを仕込み、30分間撹拌した後、イオン交換水539gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−3)を得た。
[Example 3: Preparation of active energy ray-curable aqueous resin composition (W-3)]
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube, 71 g of H 12 MDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate are added. After charging and raising the temperature to 50 ° C. under an air stream, 227 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 153 g of a 65% by mass solution of the polymer (A-3) obtained in Synthesis Example 3 (99 g as the polymer (A-3)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., 8 g of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane was added, and after stirring for 30 minutes, 539 g of ion-exchanged water was added to obtain an aqueous dispersion. It was. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-3) was obtained.
〔実施例4:活性エネルギー線硬化型水性樹脂組成物(W−4)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI69g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物221.7gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液149g(重合体(A−1)として97g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−アクリロキシプロピルトリメトキシシラン31gを仕込み、30分間撹拌した後、イオン交換水527gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−4)を得た。
[Example 4: Preparation of active energy ray-curable aqueous resin composition (W-4)]
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube, 69 g of H 12 MDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate are added. After charging and raising the temperature to 50 ° C. under an air stream, 221.7 g of PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 149 g of a 65% by mass solution of the polymer (A-1) obtained in Synthesis Example 1 (97 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., 31 g of 3-acryloxypropyltrimethoxysilane was added, and the mixture was stirred for 30 minutes, and then 527 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-4) was obtained.
〔実施例5:活性エネルギー線硬化型水性樹脂組成物(W−5)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI68g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物216gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例4で得られた重合体(A−4)の65質量%溶液145g(重合体(A−4)として94g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−メタクリロキシプロピルトリメトキシシラン(以下、「MPTMS」と略記する。)57gを仕込み、30分間撹拌した後、イオン交換水513gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−5)を得た。
[Example 5: Preparation of active energy ray-curable aqueous resin composition (W-5)]
In a four-necked flask equipped with a stirrer, thermometer, condenser, and air inlet tube, 68 g of H 12 MDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate After charging and raising the temperature to 50 ° C. under an air stream, 216 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 145 g of a 65% by mass solution of the polymer (A-4) obtained in Synthesis Example 4 (94 g as the polymer (A-4)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., and 57 g of 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as “MPTMS”) was added and stirred for 30 minutes, and then 513 g of ion-exchanged water was added to disperse the water. Got the body. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-5) was obtained.
〔実施例6:活性エネルギー線硬化型水性樹脂組成物(W−6)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、イソホロンジイソシアネート(以下、「IPDI」と略記する。)63g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物230gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.4%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液151g(重合体(A−1)として98g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−グリシドキシプロピルトリメトキシシラン24gを仕込み、30分間撹拌した後、イオン交換水513gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−6)を得た。
[Example 6: Preparation of active energy ray-curable aqueous resin composition (W-6)]
In a four-necked flask equipped with a stirrer, thermometer, cooling pipe, and air introduction pipe, 63 g of isophorone diisocyanate (hereinafter abbreviated as “IPDI”), 0.1 g of methoquinone, 3,5-dibutyl-4-hydroxytoluene After charging 1.3 g and dioctyltin dineodecanate 0.1 g and raising the temperature to 50 ° C. under an air stream, 230 g of PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.4% or less. Next, 151 g of a 65% by mass solution of the polymer (A-1) obtained in Synthesis Example 1 (98 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Subsequently, the system temperature was cooled to 30 ° C., and 24 g of 3-glycidoxypropyltrimethoxysilane was added and stirred for 30 minutes, and then 513 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-6) was obtained.
〔実施例7:活性エネルギー線硬化型水性樹脂組成物(W−7)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、IPDI62g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物226gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.4%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液149g(重合体(A−1)として97g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、p−スチリルトリメトキシシラン39gを仕込み、30分間撹拌した後、イオン交換水522gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−7)を得た。
[Example 7: Preparation of active energy ray-curable aqueous resin composition (W-7)]
A four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube was charged with 62 g of IPDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate, After raising the temperature to 50 ° C. under an air stream, 226 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.4% or less. Next, 149 g of a 65% by mass solution of the polymer (A-1) obtained in Synthesis Example 1 (97 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Subsequently, the system temperature was cooled to 30 ° C., and 39 g of p-styryltrimethoxysilane was added and stirred for 30 minutes, and then 522 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-7) was obtained.
〔実施例8:活性エネルギー線硬化型水性樹脂組成物(W−8)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、IPDI62g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物228gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.4%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液150g(重合体(A−1)として98g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、ビニルトリメトキシシラン31gを仕込み、30分間撹拌した後、イオン交換水526gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−8)を得た。
[Example 8: Preparation of active energy ray-curable aqueous resin composition (W-8)]
A four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube was charged with 62 g of IPDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate, After raising the temperature to 50 ° C. under an air stream, 228 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.4% or less. Next, 150 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (98 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., 31 g of vinyltrimethoxysilane was added and stirred for 30 minutes, and then 526 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-8) was obtained.
〔実施例9:活性エネルギー線硬化型水性樹脂組成物(W−9)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、HDI49g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物236gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.3%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液155g(重合体(A−1)として101g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−クロロプロピルトリメトキシシラン30gを仕込み、30分間撹拌した後、イオン交換水496gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−9)を得た。
[Example 9: Preparation of active energy ray-curable aqueous resin composition (W-9)]
A four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube was charged with 49 g of HDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate, After raising the temperature to 50 ° C. under an air stream, 236 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.3% or less. Next, 155 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (101 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., 30 g of 3-chloropropyltrimethoxysilane was added, and the mixture was stirred for 30 minutes, and then 496 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-9) was obtained.
〔実施例10:活性エネルギー線硬化型水性樹脂組成物(W−10)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、HDI48g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物231gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液154g(重合体(A−1)として100g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、3−メルカプトプロピルトリメトキシシラン30gを仕込み、30分間撹拌した後、イオン交換水497gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−10)を得た。
[Example 10: Preparation of active energy ray-curable aqueous resin composition (W-10)]
A four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube was charged with 48 g of HDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate, After raising the temperature to 50 ° C. under an air stream, 231 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 154 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (100 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Subsequently, the system temperature was cooled to 30 ° C., and 30 g of 3-mercaptopropyltrimethoxysilane was added and stirred for 30 minutes, and then 497 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-10) was obtained.
〔実施例11:活性エネルギー線硬化型水性樹脂組成物(W−11)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、HDI49g、H12MDI38g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.3g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物235gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液157g(重合体(A−1)として102g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、ビス(トリエトキシシリルプロピル)テトラスルフィド15gを仕込み、30分間撹拌した後、イオン交換水505gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(W−11)を得た。
[Example 11: Preparation of active energy ray-curable aqueous resin composition (W-11)]
In a four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and an air introduction tube, 49 g of HDI, 38 g of H 12 MDI, 0.1 g of methoquinone, 1.3 g of 3,5-dibutyl-4-hydroxytoluene and dioctyltin dineodecanate After charging 1 g and raising the temperature to 50 ° C. under an air stream, 235 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 157 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (102 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., 15 g of bis (triethoxysilylpropyl) tetrasulfide was added, and the mixture was stirred for 30 minutes, and then 505 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (W-11) was obtained.
〔比較例1:活性エネルギー線硬化型水性樹脂組成物(RW−1)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI71g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.4g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物229gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液154g(重合体(A−1)として100g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、イオン交換水544gを加え、水分散体を得た。さらに3−アミノプロピルトリエトキシシラン31g及び光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(RW−1)を得た。
[Comparative Example 1: Preparation of active energy ray-curable aqueous resin composition (RW-1)]
In a four-necked flask equipped with a stirrer, thermometer, condenser, and air inlet tube, 71 g of H 12 MDI, 0.1 g of methoquinone, 1.4 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate After charging and raising the temperature to 50 ° C. under an air stream, 229 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 154 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (100 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., and 544 g of ion-exchanged water was added to obtain an aqueous dispersion. Further, 31 g of 3-aminopropyltriethoxysilane and 16 g of a photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., a eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) are added, and 20 The mixture was stirred for minutes to obtain an active energy ray-curable aqueous resin composition (RW-1).
〔比較例2:活性エネルギー線硬化型水性樹脂組成物(RW−2)の調製〕
攪拌機、温度計、冷却管、空気導入管を備えた4つ口フラスコに、H12MDI71g、メトキノン0.1g、3,5−ジブチル−4−ヒドロキシトルエン1.4g及びジオクチル錫ジネオデカネート0.1gを仕込み、空気気流下50℃まで昇温した後、PETA混合物229gを仕込み、80℃まで昇温した。同温度で3時間撹拌混合した後、系中のイソシアネート百分率が1.2%以下であることを確認した。次いで、合成例1で得られた重合体(A−1)の65質量%溶液154g(重合体(A−1)として100g)を加え、同温度でさらに8時間撹拌混合し、系中のイソシアネート百分率が0.1%未満であることを確認した。次いで、系内温度を30℃まで冷却し、イオン交換水544gを加え、水分散体を得た。さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)16gを加え、20分間撹拌し、活性エネルギー線硬化型水性樹脂組成物(RW−2)を得た。
[Comparative Example 2: Preparation of active energy ray-curable aqueous resin composition (RW-2)]
In a four-necked flask equipped with a stirrer, thermometer, condenser, and air inlet tube, 71 g of H 12 MDI, 0.1 g of methoquinone, 1.4 g of 3,5-dibutyl-4-hydroxytoluene and 0.1 g of dioctyltin dineodecanate After charging and raising the temperature to 50 ° C. under an air stream, 229 g of a PETA mixture was charged and the temperature was raised to 80 ° C. After stirring and mixing at the same temperature for 3 hours, it was confirmed that the isocyanate percentage in the system was 1.2% or less. Next, 154 g of a 65 mass% solution of the polymer (A-1) obtained in Synthesis Example 1 (100 g as the polymer (A-1)) was added, and the mixture was further stirred and mixed at the same temperature for 8 hours. It was confirmed that the percentage was less than 0.1%. Next, the system temperature was cooled to 30 ° C., and 544 g of ion-exchanged water was added to obtain an aqueous dispersion. Furthermore, 16 g of photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a molar ratio of 1: 1) was added, stirred for 20 minutes, and active energy ray curable type An aqueous resin composition (RW-2) was obtained.
〔比較例3:活性エネルギー線硬化型水性樹脂組成物(RW−3)の調製〕
攪拌機、温度計及び冷却管を備えた4つ口フラスコに、合成例5で得られた重合体(RA−1)の65質量%溶液442g(重合体(RA−1)として287g)、合成例6で得られたウレタンアクリレート組成物(RB−1)500g、PETA混合物200gを仕込み、70℃で加温攪拌しながらトリエチルアミン40gを加えて攪拌混合した。次いで、イオン交換水1,379gを10回に分割投入し、さらに光重合開始剤(BASFジャパン株式会社製「イルガキュア500」、1−ヒドロキシシクロヘキシルフェニルケトンとベンゾフェノンとのモル比1:1の共融混合物)40gを混合して、活性エネルギー線硬化型水性樹脂組成物(RW−3)を得た。
[Comparative Example 3: Preparation of active energy ray-curable aqueous resin composition (RW-3)]
In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 442 g of a polymer (RA-1) 65% by mass solution obtained in Synthesis Example 5 (287 g as polymer (RA-1)), Synthesis Example 500 g of the urethane acrylate composition (RB-1) obtained in 6 and 200 g of the PETA mixture were charged, and 40 g of triethylamine was added while stirring at 70 ° C. with stirring. Next, 1,379 g of ion-exchanged water was divided into 10 times, and further a photopolymerization initiator (“Irgacure 500” manufactured by BASF Japan Ltd., eutectic with a molar ratio of 1-hydroxycyclohexyl phenyl ketone and benzophenone of 1: 1). 40 g of the mixture) was mixed to obtain an active energy ray-curable aqueous resin composition (RW-3).
なお、上記で調製した活性エネルギー線硬化型水性樹脂組成物の配合組成を表2〜4に示す。 In addition, the compounding composition of the active energy ray hardening-type aqueous resin composition prepared above is shown to Tables 2-4.
〔実施例12:活性エネルギー線硬化型水性樹脂組成物(W−1)の評価〕
実施例1で得られた活性エネルギー線硬化型水性樹脂組成物(W−1)を用いて、活性エネルギー線硬化型水性塗料としての性能を評価するため、貯蔵安定性、硬化塗膜の外観、表面硬度(鉛筆硬度)及び塗膜密着性を評価した。
[Example 12: Evaluation of active energy ray-curable aqueous resin composition (W-1)]
In order to evaluate the performance as an active energy ray-curable aqueous coating material using the active energy ray-curable aqueous resin composition (W-1) obtained in Example 1, storage stability, appearance of a cured coating film, Surface hardness (pencil hardness) and coating film adhesion were evaluated.
[貯蔵安定性の評価]
活性エネルギー線硬化型水性樹脂組成物(W−1)を200mlのガラス容器に密封して40℃で静置保存し、成分分離の状況を目視で観察して、下記の基準にしたがって、貯蔵安定性を評価した。
○:2か月間以上分離沈降なし。
△:2週間以上2か月未満で分離沈降あり。
×:2週間未満で分離沈降あり。
[Evaluation of storage stability]
The active energy ray-curable aqueous resin composition (W-1) is sealed in a 200 ml glass container and stored at 40 ° C., and the state of component separation is visually observed. Sex was evaluated.
○: No separation or settling for 2 months or more.
Δ: Separation and sedimentation occurred in 2 weeks or more and less than 2 months
X: Separation and sedimentation occurred in less than 2 weeks.
[評価用硬化塗膜の作製]
ガラス板、ABS(アクリロニトリル−ブタジエン−スチレン共重合体)板上に、乾燥後の膜厚が20μmになるように活性エネルギー線硬化型水性樹脂組成物(W−1)をスプレー塗装して、乾燥機中で60℃の温度で10分間の予備乾燥をした後、出力80W/cmの高圧水銀ランプを用いて、照射量0.8J/cm2の紫外線照射を行った。その後、23℃で24時間静置保存し、評価用硬化塗膜を作製した。
[Production of cured coating film for evaluation]
The active energy ray-curable aqueous resin composition (W-1) is spray-coated on a glass plate and an ABS (acrylonitrile-butadiene-styrene copolymer) plate so that the film thickness after drying is 20 μm, and then dried. After preliminary drying for 10 minutes at a temperature of 60 ° C. in the machine, ultraviolet irradiation with an irradiation amount of 0.8 J / cm 2 was performed using a high-pressure mercury lamp with an output of 80 W / cm. Then, it left still and stored at 23 degreeC for 24 hours, and produced the cured coating film for evaluation.
[硬化塗膜外観の評価]
上記で得られたABS板上の硬化塗膜を2灯式器具に取り付けた出力40Wの直管蛍光灯の直下2mに置き、蛍光灯の姿、形が塗膜上にどの程度明瞭に映っているかを、下記の基準にしたがって、目視により評価した。
○:2本1組になった蛍光灯が細部に至るまではっきりと確認できる。
△:2本1組になった蛍光灯が認識できるが、輪郭線がぼやけている。
×:蛍光灯の本数が判別できず、何かの光源としかわからない。
[Evaluation of appearance of cured coating film]
The cured coating on the ABS plate obtained above is placed 2m below the straight tube fluorescent lamp with an output of 40W attached to a two-lamp type instrument, and how clearly the shape and shape of the fluorescent lamp are reflected on the coating. It was visually evaluated according to the following criteria.
○: The fluorescent lamps in a set of two can be clearly confirmed up to the details.
(Triangle | delta): Although the fluorescent lamp which became a set of 2 can be recognized, the outline is blurred.
X: The number of fluorescent lamps cannot be discriminated, and it is only known as a light source.
[鉛筆硬度の測定評価]
上記で得られたガラス板上の硬化塗膜の表面について、JIS S 6006:2007に規定された鉛筆を用いて、JIS K 5600−5−4:1999に準じて、傷跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として測定した。
[Measurement evaluation of pencil hardness]
About the surface of the cured coating film on the glass plate obtained above, the hardest that did not cause scars using a pencil specified in JIS S 6006: 2007 according to JIS K 5600-5-4: 1999 The pencil hardness was measured as pencil hardness.
[塗膜密着性の評価]
上記で得られたABS板上の硬化塗膜及びガラス板上の硬化塗膜に、カッターにて1mm角で10×10個の切れ目を入れ、セロファンテープで上下左右4方向から1回ずつ剥離試験を行い、残存する目数を測定した。残存する目数が多いほど、塗膜未着性に優れている。
[Evaluation of coating film adhesion]
The cured coating film on the ABS plate and the cured coating film on the glass plate obtained above are cut by 10 × 10 in 1 mm square with a cutter, and peel test once in four directions from top, bottom, left, and right with cellophane tape. And the number of remaining eyes was measured. The greater the number of remaining eyes, the better the coating non-stick property.
〔実施例13〜22:活性エネルギー線硬化型水性樹脂組成物(W−2)〜(W−11)の評価〕
実施例12で用いた活性エネルギー線硬化型水性樹脂組成物(W−1)に代えて、実施例2〜11で得られた活性エネルギー線硬化型水性樹脂組成物(W−2)〜(W−11)をそれぞれ用いた以外は実施例12と同様に操作して、活性エネルギー線硬化型水性塗料としての性能として、貯蔵安定性、硬化塗膜の外観、表面硬度(鉛筆硬度)及び密着性を評価した。
[Examples 13 to 22: Evaluation of active energy ray-curable aqueous resin compositions (W-2) to (W-11)]
Instead of the active energy ray-curable aqueous resin composition (W-1) used in Example 12, the active energy ray-curable aqueous resin compositions (W-2) to (W) obtained in Examples 2 to 11 were used. -11) were used in the same manner as in Example 12 except that each was used as an active energy ray-curable water-based paint, as storage performance, appearance of the cured coating film, surface hardness (pencil hardness) and adhesion. Evaluated.
〔比較例4〜6:活性エネルギー線硬化型水性樹脂組成物(RW−1)〜(RW−3)の評価〕
実施例12で用いた活性エネルギー線硬化型水性樹脂組成物(W−1)に代えて、比較例1〜3で得られた活性エネルギー線硬化型水性樹脂組成物(RW−1)〜(RW−3)をそれぞれ用いた以外は実施例12と同様に操作して、活性エネルギー線硬化型水性塗料としての性能として、貯蔵安定性、硬化塗膜の外観、表面硬度(鉛筆硬度)及び密着性を評価した。
[Comparative Examples 4 to 6: Evaluation of active energy ray-curable aqueous resin compositions (RW-1) to (RW-3)]
Instead of the active energy ray-curable aqueous resin composition (W-1) used in Example 12, the active energy ray-curable aqueous resin compositions (RW-1) to (RW) obtained in Comparative Examples 1 to 3 were used. -3) were used in the same manner as in Example 12 except that each of them was used as an active energy ray-curable water-based paint, as storage performance, appearance of the cured coating film, surface hardness (pencil hardness) and adhesion. Evaluated.
実施例12〜22及び比較例4〜6の評価結果を表5〜7に示す。 The evaluation results of Examples 12 to 22 and Comparative Examples 4 to 6 are shown in Tables 5 to 7.
表5〜7に示した評価結果から、本発明の活性エネルギー線硬化型水性樹脂組成物は優れた貯蔵安定性を有しており、ガラス基材との高い密着性を有する高硬度塗膜が得られることが分かった。 From the evaluation results shown in Tables 5 to 7, the active energy ray-curable aqueous resin composition of the present invention has excellent storage stability, and a high-hardness coating film having high adhesion to the glass substrate is obtained. It turns out that it is obtained.
一方、比較例1は、本発明の必須工程である樹脂組成物(X)と、アルコキシシリル基を有する化合物(Y)とを含有する混合物を、水媒体中で分散させる工程を経ない例、具体的には、樹脂組成物(X)を水媒体中で分散させた後に、アルコキシシリル基を有する化合物(Y)を混合した例であるが、貯蔵安定性及び硬化塗膜の外観が不良であった(比較例5)。 On the other hand, Comparative Example 1 is an example in which the step of dispersing the mixture containing the resin composition (X), which is an essential step of the present invention, and the compound (Y) having an alkoxysilyl group in an aqueous medium, Specifically, although the resin composition (X) is dispersed in an aqueous medium and then the compound (Y) having an alkoxysilyl group is mixed, the storage stability and the appearance of the cured coating film are poor. (Comparative Example 5).
比較例2は、本発明の必須原料であるアルコキシシリル基を有する化合物(Y)を用いなかった例であるが、硬化塗膜のガラスへの密着性が不良であった(比較例5)。 Although the comparative example 2 is an example which did not use the compound (Y) which has the alkoxy silyl group which is an essential raw material of this invention, the adhesiveness to the glass of a cured coating film was unsatisfactory (comparative example 5).
比較例3は、本発明の必須原料であるポリオキシアルキレン基を有するアクリル単量体(a1)を用いず、アミンで中和したカルボキシル基を有する重合体を用い、さらに、アルコキシシリル基を有する化合物(Y)を用いなかった例であるが、硬化塗膜の外観がやや劣り、ガラスへの密着性が不良であった(比較例6)。 Comparative Example 3 does not use the acrylic monomer (a1) having a polyoxyalkylene group which is an essential raw material of the present invention, uses a polymer having a carboxyl group neutralized with an amine, and further has an alkoxysilyl group. Although it is an example which did not use a compound (Y), the external appearance of the cured coating film was a little inferior and the adhesiveness to glass was bad (comparative example 6).
Claims (6)
品。 6. An article coated with the active energy ray-curable water-based paint according to claim 5.
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---|---|---|---|---|
JP2018127535A (en) * | 2017-02-08 | 2018-08-16 | アイカ工業株式会社 | Aqueous coating material composition imparting designability to outer wall |
CN113004782A (en) * | 2021-03-06 | 2021-06-22 | 高州市名洋化工有限公司 | Photocureable coating and preparation method and application thereof |
JP7482669B2 (en) | 2019-04-18 | 2024-05-14 | エスケー イノベーション カンパニー リミテッド | New silicon compounds |
Families Citing this family (2)
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---|---|---|---|---|
WO2015108544A1 (en) | 2014-01-16 | 2015-07-23 | Hewlett-Packard Development Company, L.P. | Polymeric powder composition for three-dimensional (3d) printing |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002012797A (en) * | 2000-04-27 | 2002-01-15 | Dainippon Ink & Chem Inc | Active energy ray curable aqueous coating composition, coated metal material having cured film of the composition, manufacturing method and welding method of coated metal material |
JP2007002048A (en) * | 2005-06-22 | 2007-01-11 | Nippon Paint Co Ltd | Aqueous clear coating composition and method for forming clear film |
JP2012172110A (en) * | 2011-02-23 | 2012-09-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Energy ray-curable resin composition |
-
2013
- 2013-03-29 JP JP2013072529A patent/JP6135915B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002012797A (en) * | 2000-04-27 | 2002-01-15 | Dainippon Ink & Chem Inc | Active energy ray curable aqueous coating composition, coated metal material having cured film of the composition, manufacturing method and welding method of coated metal material |
JP2007002048A (en) * | 2005-06-22 | 2007-01-11 | Nippon Paint Co Ltd | Aqueous clear coating composition and method for forming clear film |
JP2012172110A (en) * | 2011-02-23 | 2012-09-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Energy ray-curable resin composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018127535A (en) * | 2017-02-08 | 2018-08-16 | アイカ工業株式会社 | Aqueous coating material composition imparting designability to outer wall |
JP7482669B2 (en) | 2019-04-18 | 2024-05-14 | エスケー イノベーション カンパニー リミテッド | New silicon compounds |
CN113004782A (en) * | 2021-03-06 | 2021-06-22 | 高州市名洋化工有限公司 | Photocureable coating and preparation method and application thereof |
CN113004782B (en) * | 2021-03-06 | 2022-04-29 | 高州市名洋化工有限公司 | Photocureable coating and preparation method and application thereof |
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