JP2011006558A - Photocurable resin composition dispersed in water-based medium - Google Patents
Photocurable resin composition dispersed in water-based medium Download PDFInfo
- Publication number
- JP2011006558A JP2011006558A JP2009150343A JP2009150343A JP2011006558A JP 2011006558 A JP2011006558 A JP 2011006558A JP 2009150343 A JP2009150343 A JP 2009150343A JP 2009150343 A JP2009150343 A JP 2009150343A JP 2011006558 A JP2011006558 A JP 2011006558A
- Authority
- JP
- Japan
- Prior art keywords
- ethylenically unsaturated
- resin composition
- photocurable resin
- unsaturated monomer
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 77
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 20
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 239000012736 aqueous medium Substances 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 31
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical group C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 10
- 238000012719 thermal polymerization Methods 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- -1 coatings Substances 0.000 description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- 238000007259 addition reaction Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 20
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 12
- 230000009257 reactivity Effects 0.000 description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 9
- 239000011976 maleic acid Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 5
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 5
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 5
- 239000001530 fumaric acid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- UHMARZNHEMRXQH-UHFFFAOYSA-N 3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21 UHMARZNHEMRXQH-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WCCOKHCBAKSJAX-UHFFFAOYSA-N C(C(=C)C)(=O)OCCN(C)C.N(CCO)CCO Chemical compound C(C(=C)C)(=O)OCCN(C)C.N(CCO)CCO WCCOKHCBAKSJAX-UHFFFAOYSA-N 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 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 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、紫外線などの活性エネルギーによる硬化性樹脂組成物に関し、特に硬度、密着性、耐薬品性に優れ、短時間で硬化する活性エネルギー線硬化性塗料、インキ、コーティング剤等への好適な水系媒体に分散した光硬化性樹脂組成物に関するものである。 The present invention relates to a curable resin composition using active energy such as ultraviolet rays, and is particularly suitable for active energy ray-curable paints, inks, coating agents and the like that are excellent in hardness, adhesion, and chemical resistance and are cured in a short time. The present invention relates to a photocurable resin composition dispersed in an aqueous medium.
紫外線などの光照射により硬化する塗料、コーティング、インキ等は従来のエポキシ樹脂、メラミン樹脂等の熱硬化性樹脂を使用するシステムに比べて省エネルギー、省スペース、短時間硬化、さらには皮膜強度が優れており、特に保護コート剤として表面硬度、耐スクラッチ性、耐薬品性が要求される用途に広く適用できる。 Paints, coatings, inks, etc. that are cured by irradiation with light such as ultraviolet rays are superior in energy saving, space saving, short-time curing, and film strength compared to systems using thermosetting resins such as conventional epoxy resins and melamine resins. In particular, it can be widely applied to applications requiring surface hardness, scratch resistance and chemical resistance as a protective coating agent.
従来の光硬化性樹脂は、光硬化性モノマー、または、オリゴマーと光重合開始剤、及び、粘度調節のための希釈モノマーを混合した無溶剤型及び溶剤により希釈する溶剤系が一般的である。しかし、昨今の環境問題において、溶剤を使用することは、適切ではない。 Conventional photocurable resins are generally a solvent-free type in which a photocurable monomer or an oligomer, a photopolymerization initiator, and a dilution monomer for viscosity adjustment are mixed, and a solvent system that is diluted with a solvent. However, in recent environmental problems, it is not appropriate to use a solvent.
この問題の解決方法として、光硬化性ポリマーを水系化することが提案されている（特許文献１及び特許文献２）。光硬化性ポリマーは、使用時に光重合開始剤を後添加する必要があり、光重合開始剤の形態としては、液体と固体がある。形態が液体である光重合開始剤は、水系化した光硬化性ポリマーに後添加する場合、容易に混和することができる。しかし、形態が固体である光重合開始剤を水系化した光硬化性ポリマーに後添加する場合は、固体状態での混和は不可能である。そこで、通常、溶剤又は硬化性モノマーで光重合開始剤を溶解してから添加するが、その添加量は、光硬化性ポリマーに対し、５質量部程度であった（特許文献３）。その光重合開始剤量であると、例えば、光硬化性塗膜が厚膜になった場合、光重合開始剤が不足し、光硬化性ポリマーの光硬化性を十分に発揮する添加量ではない。また、光硬化性を向上させるため、添加量を多くすると、液がすぐにゲル化し、使用できないなどの問題点があった。 As a solution to this problem, it has been proposed to make a photocurable polymer aqueous (Patent Document 1 and Patent Document 2). It is necessary to add a photopolymerization initiator after use for the photocurable polymer, and the photopolymerization initiator includes liquid and solid forms. The photopolymerization initiator having a liquid form can be easily mixed when added to the water-based photocurable polymer. However, when a photopolymerization initiator having a solid form is added later to a water-based photocurable polymer, mixing in a solid state is impossible. Therefore, the photopolymerization initiator is usually added after dissolving with a solvent or a curable monomer, but the addition amount was about 5 parts by mass with respect to the photocurable polymer (Patent Document 3). If the amount of the photopolymerization initiator is, for example, when the photocurable coating film becomes thick, the photopolymerization initiator is insufficient, and it is not an addition amount that sufficiently exhibits the photocurability of the photocurable polymer. . Further, when the addition amount is increased in order to improve the photocurability, there is a problem that the liquid immediately gels and cannot be used.
本発明は、従来技術である水系媒体に分散した光硬化性樹脂への形態が固体である光重合開始剤添加方法及び光硬化性の上記問題点に鑑み、紫外線などの活性エネルギーによる硬化に用いることができ、光硬化性が効率的で、かつ液安定性に優れる水系媒体に分散した光硬化性樹脂組成物を提供することを目的とする。 The present invention is used for curing by an active energy such as ultraviolet rays in view of the above-mentioned problems of the photopolymerization initiator addition method in which the form to a photocurable resin dispersed in an aqueous medium, which is a conventional technique, is solid, and the photocurability. It is an object of the present invention to provide a photocurable resin composition that is dispersed in an aqueous medium that can be photocured efficiently and has excellent liquid stability.
本発明者らは、上記の課題を解決すべく鋭意研究した結果、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
本発明は、３０℃、１ａｔｍで固体である光重合開始剤をエチレン性不飽和単量体に溶解させた後、熱重合開始剤を用いて該エチレン性不飽和単量体及び官能基を含有するエチレン性不飽和単量体を重合させ、得られた重合体の官能基にエチレン性不飽和基を有する化合物を付加反応させることで１分子中に２つ以上のエチレン性不飽和基を含有させた、水系媒体に分散した光硬化性樹脂組成物に関する。 The present invention contains a photopolymerization initiator that is solid at 30 ° C. and 1 atm in an ethylenically unsaturated monomer, and then contains the ethylenically unsaturated monomer and a functional group using a thermal polymerization initiator. Containing two or more ethylenically unsaturated groups in one molecule by polymerizing the ethylenically unsaturated monomer to be reacted and adding a compound having an ethylenically unsaturated group to the functional group of the resulting polymer. The photocurable resin composition dispersed in an aqueous medium.
前記重合は、界面活性剤存在下における乳化重合であることが好ましい。 The polymerization is preferably emulsion polymerization in the presence of a surfactant.
また、本発明は、３０℃、１ａｔｍで固体である光重合開始剤をエチレン性不飽和単量体に溶解させた後、熱重合開始剤を用いて該エチレン性不飽和単量体を重合させた重合体に、１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物を混合させた、水系媒体に分散した光硬化性樹脂組成物に関する。 In the present invention, a photopolymerization initiator that is solid at 30 ° C. and 1 atm is dissolved in an ethylenically unsaturated monomer, and then the ethylenically unsaturated monomer is polymerized using a thermal polymerization initiator. The present invention relates to a photocurable resin composition dispersed in an aqueous medium, in which a polyfunctional compound containing two or more ethylenically unsaturated groups per molecule is mixed with the polymer.
前記重合は、エチレン性不飽和単量体、及びカルボキシル基を含有するエチレン性不飽和単量体を重合させるものであり、得られた重合体のカルボキシル基を塩基で中和することで重合体及び多官能化合物を水系媒体に分散させたものであることが好ましい。 The polymerization is a polymerization of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer containing a carboxyl group, and the polymer is obtained by neutralizing the carboxyl group of the obtained polymer with a base. It is preferable that the polyfunctional compound is dispersed in an aqueous medium.
該重合体にエチレン性不飽和基を有する化合物を付加反応することにより得られるものであることが好ましい。 The polymer is preferably obtained by addition reaction of a compound having an ethylenically unsaturated group.
前記光重合開始剤は、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンであることが好ましい。 The photopolymerization initiator is preferably 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.
前記光重合開始剤は、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンであることが好ましい。 The photopolymerization initiator is preferably 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
前記光重合開始剤は、前記光硬化性樹脂組成物の全固形分１００質量部に対し、８〜３５質量部であることが好ましい。 It is preferable that the said photoinitiator is 8-35 mass parts with respect to 100 mass parts of total solid of the said photocurable resin composition.
さらに、本発明は、３０℃、１ａｔｍで固体である光重合開始剤をエチレン性不飽和単量体に溶解させた後、熱重合開始剤を用いて該エチレン性不飽和単量体を重合させて得られる、水系媒体に分散した光硬化用樹脂組成物に関する。 Furthermore, the present invention comprises dissolving a photopolymerization initiator that is solid at 30 ° C. and 1 atm in an ethylenically unsaturated monomer, and then polymerizing the ethylenically unsaturated monomer using a thermal polymerization initiator. And a photocurable resin composition dispersed in an aqueous medium.
本発明の水系媒体に分散した光硬化性樹脂組成物は、紫外線などの活性エネルギーによる硬化反応に用いられ、光硬化性が非常に効率的であり、硬化反応時の臭気発生が極めて少なく、作業環境の悪化を抑制でき、優れた物性を持つ光硬化物が得られる。また、貯蔵安定性に優れ、作業性に優れる。 The photo-curable resin composition dispersed in the aqueous medium of the present invention is used for a curing reaction by active energy such as ultraviolet rays, has a very efficient photo-curing property, and generates very little odor during the curing reaction. It is possible to suppress the deterioration of the environment and obtain a photocured product having excellent physical properties. Moreover, it is excellent in storage stability and workability.
以下、本発明を詳細に説明する。本発明で用いられる、形態が固体である光重合開始剤とは、活性エネルギー線によりラジカルを発生する光増感性官能基を有し、３０℃、１ａｔｍで固体である化合物である。 Hereinafter, the present invention will be described in detail. The photopolymerization initiator having a solid form used in the present invention is a compound having a photosensitizing functional group that generates radicals by active energy rays and is solid at 30 ° C. and 1 atm.
３０℃、１ａｔｍで形態が固体である光重合開始剤としては、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムなどを挙げることができ、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンが光硬化性の観点から好ましい。 Examples of the photopolymerization initiator that is solid at 30 ° C. and 1 atm include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η 5 -2,4-cyclo And pentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Roxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) Phenyl] -2-morpholinopropan-1-one is preferred from the viewpoint of photocurability.
本発明の水系媒体に分散した光硬化性樹脂組成物中の形態が固体である光重合開始剤の量は、光硬化性の観点から水系媒体に分散した光硬化性樹脂組成物の全固形分１００質量部に対し、８〜３５質量部が望ましく、１０〜３０質量部がさらに望ましい。８質量部より少ないと光硬化性が十分でなく、３５質量部より多いと水系媒体に分散した光硬化性樹脂組成物の重合途中にゲル化する傾向にある。 The amount of the photopolymerization initiator that is solid in the photocurable resin composition dispersed in the aqueous medium of the present invention is the total solid content of the photocurable resin composition dispersed in the aqueous medium from the viewpoint of photocurability. 8-35 mass parts is desirable with respect to 100 mass parts, and 10-30 mass parts is more desirable. When the amount is less than 8 parts by mass, the photocurability is not sufficient. When the amount is more than 35 parts by mass, the photocurable resin composition dispersed in the aqueous medium tends to gel during polymerization.
形態が固体である光重合開始剤を溶解させるのに用いられるエチレン性不飽和単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、アクリロニトリル、スチレン、スチレン誘導体、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン、エチレン、プロピレン、ブチレン、イソブチレン等を使用することができる。これらエチレン性不飽和単量体は、単独であるいは組み合わせて使用することができる。本発明の水系媒体に分散した光硬化性樹脂組成物のガラス転移温度は、特に制限されない。 Examples of the ethylenically unsaturated monomer used to dissolve the photopolymerization initiator having a solid form include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylonitrile, styrene, styrene Derivatives, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, ethylene, propylene, butylene, isobutylene, and the like can be used. These ethylenically unsaturated monomers can be used alone or in combination. The glass transition temperature of the photocurable resin composition dispersed in the aqueous medium of the present invention is not particularly limited.
本発明では、３０℃、１ａｔｍで固体である光重合開始剤をエチレン性不飽和単量体に溶解させた後、熱重合開始剤を用いて該エチレン性不飽和単量体及び官能基を含有するエチレン性不飽和単量体を重合させることで得られる重合体の官能基に、エチレン性不飽和基を有する化合物を付加反応させることで１分子中に２つ以上のエチレン性不飽和基を含有させた、水系媒体に分散した光硬化性樹脂組成物を得ることができる。なかでも、該重合を、界面活性剤存在下における乳化重合により行うことが、重合安定性、光硬化性の樹脂組成物の高不揮発分化、高分子量化、低粘度化の点で好ましい。 In the present invention, the photopolymerization initiator that is solid at 30 ° C. and 1 atm is dissolved in the ethylenically unsaturated monomer, and then the ethylenically unsaturated monomer and the functional group are contained using the thermal polymerization initiator. Two or more ethylenically unsaturated groups are added to one molecule by addition reaction of a compound having an ethylenically unsaturated group to the functional group of the polymer obtained by polymerizing the ethylenically unsaturated monomer. A photocurable resin composition dispersed in an aqueous medium can be obtained. Among these, the polymerization is preferably carried out by emulsion polymerization in the presence of a surfactant from the viewpoints of polymerization stability, high non-volatile differentiation, high molecular weight, and low viscosity of the photocurable resin composition.
界面活性剤としては、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び共重合性乳化剤が使用できる。また、これらの界面活性剤は、単独であるいは二種以上を組み合わせて使用することができる。本発明の水系媒体に分散した光硬化性樹脂組成物の界面活性剤量は、特に制限されない。 As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable emulsifiers can be used. These surfactants can be used alone or in combination of two or more. The amount of the surfactant in the photocurable resin composition dispersed in the aqueous medium of the present invention is not particularly limited.
乳化重合においては、熱重合開始剤を使用するのが好ましく、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、アゾ系化合物等が使用される。また、これらと還元剤の併用によるレドックス系開始剤を使用することもできる。 In the emulsion polymerization, it is preferable to use a thermal polymerization initiator, and persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, azo compounds and the like are used. Moreover, the redox initiator by using these together with a reducing agent can also be used.
乳化重合法としては、一括して仕込み重合する方法、各成分を連続供給しながら重合する方法などが適用できる。重合は通常３０〜８５℃の温度で攪拌下に行われる。 As the emulsion polymerization method, a method of batch polymerization and a method of polymerization while continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 30 to 85 ° C. with stirring.
乳化重合で得られる重合体にエチレン性不飽和基を有する化合物を付加反応させる方法として、カルボキシル基を含有するエチレン性不飽和単量体またはグリシジル基を含有するエチレン性不飽和単量体を前記エチレン性不飽和単量体と共重合させることで各反応性官能基を重合体に導入し、それぞれの反応性官能基に反応し得る官能基を含有するエチレン性不飽和基を有する化合物を付加反応させる方法を挙げることができる。 As a method for adding a compound having an ethylenically unsaturated group to a polymer obtained by emulsion polymerization, an ethylenically unsaturated monomer containing a carboxyl group or an ethylenically unsaturated monomer containing a glycidyl group is used. Each reactive functional group is introduced into the polymer by copolymerizing with an ethylenically unsaturated monomer, and a compound having an ethylenically unsaturated group containing a functional group capable of reacting with each reactive functional group is added. The method of making it react can be mentioned.
カルボキシル基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物として、グリシジル基を含有するエチレン性不飽和基を有する化合物が挙げられる。 Examples of the compound having an ethylenically unsaturated group capable of addition reaction with an ethylenically unsaturated monomer containing a carboxyl group include compounds having an ethylenically unsaturated group containing a glycidyl group.
カルボキシル基を含有するエチレン性不飽和単量体としては、アクリル酸、メタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、２−メチルマレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩或いはそれらの混合物を挙げられる。なかでも、光硬化性樹脂組成物の貯蔵安定性、付加反応の反応性、重合安定性、光硬化性の点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましい。これらのカルボキシル基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of the ethylenically unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, Tetrahydrophthalic anhydrides, their metal salts, ammonium salts or mixtures thereof. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred from the viewpoints of storage stability of the photocurable resin composition, reactivity of addition reaction, polymerization stability, and photocurability. These ethylenically unsaturated monomers containing a carboxyl group can be used alone or in combination.
グリシジル基を含有するエチレン性不飽和基を有する化合物としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられる。なかでも、付加反応の反応性、光硬化性の点から、グリシジルメタクリレートが好ましい。これらのグリシジル基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Examples of the compound having an ethylenically unsaturated group containing a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl. And methacrylate. Of these, glycidyl methacrylate is preferred from the viewpoint of the reactivity of the addition reaction and photocurability. These compounds having an ethylenically unsaturated group containing a glycidyl group can be used alone or in combination.
グリシジル基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物としては、カルボキシル基を含有するエチレン性不飽和基を有する化合物が挙げられる。 Examples of the compound having an ethylenically unsaturated group capable of addition reaction with an ethylenically unsaturated monomer containing a glycidyl group include compounds having an ethylenically unsaturated group containing a carboxyl group.
グリシジル基を含有するエチレン性不飽和単量体としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられる。なかでも、付加反応の反応性、重合安定性、光硬化性の点から、グリシジルメタクリレートが好ましい。これらのグリシジル基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of the ethylenically unsaturated monomer containing a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Etc. Of these, glycidyl methacrylate is preferable from the viewpoint of the reactivity of the addition reaction, polymerization stability, and photocurability. These ethylenically unsaturated monomers containing a glycidyl group can be used alone or in combination.
カルボキシル基を含有するエチレン性不飽和基を有する化合物としては、アクリル酸、メタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、２−メチルマレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩或いはそれらの混合物を挙げられる。なかでも、付加反応の反応性、光硬化性の点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましい。これらのカルボキシル基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Compounds having an ethylenically unsaturated group containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid , Tetrahydrophthalic anhydride, their metal salts, ammonium salts or mixtures thereof. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred from the viewpoint of the reactivity of addition reaction and photocurability. These compounds having an ethylenically unsaturated group containing a carboxyl group can be used alone or in combination.
通常、これらの付加反応は、一般に用いられる周知の触媒存在下に加熱することで容易に行うことができる。 Usually, these addition reactions can be easily carried out by heating in the presence of a commonly used catalyst.
カルボキシル基やグリシジル基を含有するエチレン性不飽和単量体のような、乳化重合により得られる重合体に反応性官能基を導入するために用いられる、官能基を含有するエチレン性不飽和単量体は、重合に用いられる全てのエチレン性不飽和単量体１００質量部に対して、５〜５０質量部使用することが好ましい。５質量部より少ないと付加反応させるエチレン性不飽和基を有する化合物が減少し、光硬化性が充分でなく、５０質量部より多いと、乳化重合中にゲル化する傾向にある。 An ethylenically unsaturated monomer containing a functional group used to introduce a reactive functional group into a polymer obtained by emulsion polymerization, such as an ethylenically unsaturated monomer containing a carboxyl group or a glycidyl group The body is preferably used in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of all ethylenically unsaturated monomers used for polymerization. When the amount is less than 5 parts by mass, the compound having an ethylenically unsaturated group to be subjected to addition reaction is decreased, and the photocurability is not sufficient. When the amount is more than 50 parts by mass, gelation tends to occur during emulsion polymerization.
また、乳化重合により得られる重合体の反応性官能基に付加反応させるエチレン性不飽和基を有する化合物は、固形分で重合体１００質量部に対して、５〜５０質量部を使用することが好ましい。５質量部より少ないと、光硬化性が充分でなく、５０質量部より多いと付加反応中にゲル化する傾向にある。 Moreover, the compound which has an ethylenically unsaturated group made to addition-react with the reactive functional group of the polymer obtained by emulsion polymerization uses 5-50 mass parts with respect to 100 mass parts of polymers by solid content. preferable. If it is less than 5 parts by mass, the photocurability is not sufficient, and if it is more than 50 parts by mass, it tends to gel during the addition reaction.
さらに、本発明では３０℃、１ａｔｍで固体である光重合開始剤をエチレン性不飽和単量体に溶解させた後、熱重合開始剤を用いて該エチレン性不飽和単量体を重合させた重合体に、１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物を混合させた、水系媒体に分散した光硬化性樹脂組成物を得ることも可能である。重合体及び多官能化合物を水系媒体に分散させる方法としては、前記重合がエチレン性不飽和単量体及びカルボキシル基を含有するエチレン性不飽和単量体を重合させるものであり、得られた重合体のカルボキシル基を塩基で中和した後に水系媒体を加えて転相させる方法が、乳化剤を使用しないため、耐水性、耐温水性の点から、好ましい。 Furthermore, in this invention, after dissolving the photoinitiator which is solid at 30 degreeC and 1 atm in an ethylenically unsaturated monomer, this ethylenically unsaturated monomer was polymerized using the thermal polymerization initiator. It is also possible to obtain a photocurable resin composition dispersed in an aqueous medium, in which a polyfunctional compound containing two or more ethylenically unsaturated groups per molecule is mixed with a polymer. As a method for dispersing the polymer and the polyfunctional compound in an aqueous medium, the polymerization is performed by polymerizing an ethylenically unsaturated monomer and an ethylenically unsaturated monomer containing a carboxyl group. A method in which an aqueous medium is added to the phase after neutralizing the carboxyl group of the coalescence with a base is preferable from the viewpoint of water resistance and warm water resistance because an emulsifier is not used.
カルボキシル基を含有するエチレン性不飽和単量体としては、アクリル酸、メタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、２−メチルマレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩或いはそれらの混合物を挙げられる。なかでも、光硬化性樹脂組成物の貯蔵安定性、付加反応の反応性、重合安定性、光硬化性の点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましい。これらのカルボキシル基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of the ethylenically unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, Tetrahydrophthalic anhydrides, their metal salts, ammonium salts or mixtures thereof. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred from the viewpoints of storage stability of the photocurable resin composition, reactivity of addition reaction, polymerization stability, and photocurability. These ethylenically unsaturated monomers containing a carboxyl group can be used alone or in combination.
カルボキシル基を含有するエチレン性不飽和単量体は、光重合開始剤を溶解させたエチレン性不飽和単量体１００質量部に対して５〜５０質量部使用することが好ましい。５質量部より少ないと、転相することが不可能、もしくは、光硬化性樹脂組成物の貯蔵安定性が低下し、５０質量部より多いと得られる水系媒体に分散した光硬化性樹脂組成物が高粘度となり、使用時に弊害となる傾向にある。 The ethylenically unsaturated monomer containing a carboxyl group is preferably used in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer in which the photopolymerization initiator is dissolved. When the amount is less than 5 parts by mass, phase inversion is impossible, or the storage stability of the photocurable resin composition is lowered. When the amount is more than 50 parts by mass, the photocurable resin composition dispersed in an aqueous medium is obtained. Tends to be harmful when used.
本発明における、転相させる重合体の重合に用いる熱重合開始剤としては、通常使用されるものであれば特に限定はなく、例えば、アゾビスイソブチロニトリル、アゾビス（２−メチルブチロニトリル）、過酸化ベンゾイル等が挙げられる。 In the present invention, the thermal polymerization initiator used for the polymerization of the polymer to be phase-inverted is not particularly limited as long as it is usually used. For example, azobisisobutyronitrile, azobis (2-methylbutyronitrile) ), Benzoyl peroxide and the like.
本発明における、転相させる重合体の重合の方法としては、一括して仕込み重合する方法、各成分を連続供給しながら重合する方法などが適用できる。重合は通常３０〜１５０℃の温度で攪拌下に行われる。 As a method for polymerizing the polymer to be phase-inverted in the present invention, a method of batch polymerization and a method of polymerization while continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 30 to 150 ° C. with stirring.
上記の１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物は、エチレン性不飽和単量体及びエチレン性不飽和オリゴマーの双方を含むものである。１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物の例としては、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、ネオペンチルグリコールジ（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、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコール（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、アリル化シクロへキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性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。オリゴマーとしては、ウレタンアクリレート、エポキシアクリレート、ポリエーテルアクリレート等が挙げられる。なかでも、活性エネルギーによる硬化性、耐擦傷性、耐汚染性、耐割れ性、低毒性の点から、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレートが好ましい。これらの１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物の使用範囲としては、水系媒体に分散した光硬化樹脂組成物の固形分全量対して５〜９０質量部が望ましい。５質量部未満であると、硬化性が充分でなく、９０質量部より多いと、水系媒体に分散した光硬化性樹脂組成物の貯蔵安定性が悪くなる傾向にある。 The polyfunctional compound containing two or more ethylenically unsaturated groups in one molecule includes both an ethylenically unsaturated monomer and an ethylenically unsaturated oligomer. Examples of polyfunctional compounds containing two or more ethylenically unsaturated groups in one molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclo Pentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propion Examples include acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Examples of the oligomer include urethane acrylate, epoxy acrylate, and polyether acrylate. Of these, dipentaerythritol hexaacrylate and pentaerythritol tetraacrylate are preferred from the viewpoints of curability by active energy, scratch resistance, stain resistance, crack resistance, and low toxicity. The range of use of the polyfunctional compound containing two or more ethylenically unsaturated groups in one molecule is preferably 5 to 90 parts by mass with respect to the total solid content of the photocurable resin composition dispersed in the aqueous medium. . When it is less than 5 parts by mass, the curability is not sufficient, and when it is more than 90 parts by mass, the storage stability of the photocurable resin composition dispersed in the aqueous medium tends to deteriorate.
転相させる重合体に１分子中に２つ以上のエチレン性不飽和基を含有する多官能化合物を混合させるだけでなく、さらにエチレン性不飽和基を有する化合物を付加反応させることが、光硬化性樹脂組成物を硬化させた膜が硬度にすぐれ、耐擦傷性、耐汚染性の点で好ましい。エチレン性不飽和基を有する化合物を付加反応させる方法として、（Ａ）イソシアネート基を含有するエチレン性不飽和単量体、（Ｂ）ヒドロキシル基を含有するエチレン性不飽和単量体、（Ｃ）カルボキシル基を含有するエチレン性不飽和単量体、（Ｄ）グリシジル基を含有するエチレン性不飽和単量体をエチレン性不飽和単量体と共重合させることで各反応性官能基を重合体に導入し、それぞれの反応性官能基に反応し得る官能基を含有するエチレン性不飽和基を有する化合物を付加反応させる方法を挙げることができる。 In addition to mixing a polyfunctional compound containing two or more ethylenically unsaturated groups in one molecule with the polymer to be phase-inverted, it is possible to carry out an addition reaction with a compound having an ethylenically unsaturated group. A film obtained by curing the conductive resin composition is excellent in hardness and preferable in terms of scratch resistance and stain resistance. As a method for addition reaction of a compound having an ethylenically unsaturated group, (A) an ethylenically unsaturated monomer containing an isocyanate group, (B) an ethylenically unsaturated monomer containing a hydroxyl group, (C) Polymerizing each reactive functional group by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and (D) an ethylenically unsaturated monomer containing a glycidyl group with the ethylenically unsaturated monomer And an addition reaction of a compound having an ethylenically unsaturated group containing a functional group capable of reacting with each reactive functional group.
（Ａ）イソシアネート基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物として、ヒドロキシル基を含有するエチレン性不飽和基を有する化合物が挙げられる。 (A) As a compound which has an ethylenically unsaturated group which can carry out addition reaction with the ethylenically unsaturated monomer containing an isocyanate group, the compound which has an ethylenically unsaturated group containing a hydroxyl group is mentioned.
イソシアネート基を含有するエチレン性不飽和単量体としては、２−イソシアナートエチル（メタ）アクリレート、３−イソシアナートプロピル（メタ）アクリレートなどを挙げることができる。なかでも、付加反応の反応性、光硬化性の点から、２−イソシアナートエチルアクリレート、２−イソシアナートエチルメタクリレートが好ましい。これらのイソシアネート基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of the ethylenically unsaturated monomer containing an isocyanate group include 2-isocyanatoethyl (meth) acrylate and 3-isocyanatopropyl (meth) acrylate. Of these, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate are preferred from the viewpoint of the reactivity of the addition reaction and photocurability. These ethylenically unsaturated monomers containing isocyanate groups can be used alone or in combination.
ヒドロキシル基を含有するエチレン性不飽和基を有する化合物としては、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレート、ポリテトラメチレングリコールモノアクリレート、ポリエチレングリコールポリテトラメチレングリコールモノアクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリテトラメチレングリコールモノメタクリレート、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート等が挙げられる。なかでも、付加反応の反応性、重合安定性、光硬化性の点から、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレートが好ましい。これらのヒドロキシル基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Examples of the compound having an ethylenically unsaturated group containing a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, polyethylene glycol polytetramethylene Glycol monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, polyethylene Glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred from the viewpoint of the reactivity of the addition reaction, polymerization stability, and photocurability. These compounds having an ethylenically unsaturated group containing a hydroxyl group can be used alone or in combination.
（Ｂ）ヒドロキシル基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物として、イソシアネート基を含有するエチレン性不飽和基を有する化合物を挙げられる。 (B) As a compound which has an ethylenically unsaturated group which can carry out addition reaction with the ethylenically unsaturated monomer containing a hydroxyl group, the compound which has an ethylenically unsaturated group containing an isocyanate group is mentioned.
ヒドロキシル基を含有するエチレン性不飽和単量体としては、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレート、ポリテトラメチレングリコールモノアクリレート、ポリエチレングリコールポリテトラメチレングリコールモノアクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリテトラメチレングリコールモノメタクリレート、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート等が挙げられる。なかでも、付加反応の反応性、重合安定性、光硬化性の点から、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレートが好ましい。これらのヒドロキシル基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of ethylenically unsaturated monomers containing hydroxyl groups include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, polyethylene glycol polytetramethylene glycol Monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, polyethyleneglycol Polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred from the viewpoint of the reactivity of the addition reaction, polymerization stability, and photocurability. These ethylenically unsaturated monomers containing hydroxyl groups can be used alone or in combination.
イソシアネート基を含有するエチレン性不飽和基を有する化合物としては、２−イソシアナートエチル（メタ）アクリレート、３−イソシアナートプロピル（メタ）アクリレートなどを挙げることができる。なかでも、付加反応の反応性、光硬化性の点から、２−イソシアナートエチルアクリレート、２−イソシアナートエチルメタクリレートが好ましい。これらのイソシアネート基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Examples of the compound having an ethylenically unsaturated group containing an isocyanate group include 2-isocyanatoethyl (meth) acrylate and 3-isocyanatopropyl (meth) acrylate. Of these, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate are preferred from the viewpoint of the reactivity of the addition reaction and photocurability. These compounds having an ethylenically unsaturated group containing an isocyanate group can be used alone or in combination.
（Ｃ）カルボキシル基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物として、グリシジル基を含有するエチレン性不飽和基を有する化合物が挙げられる。 (C) As the compound having an ethylenically unsaturated group capable of addition reaction with an ethylenically unsaturated monomer containing a carboxyl group, a compound having an ethylenically unsaturated group containing a glycidyl group can be mentioned.
カルボキシル基を含有するエチレン性不飽和単量体としては、すでに述べたとおり、アクリル酸、メタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、２−メチルマレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩或いはそれらの混合物を挙げられる。 As described above, as the ethylenically unsaturated monomer containing a carboxyl group, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid , Tetrahydrophthalic acid, tetrahydrophthalic anhydride, their metal salts, ammonium salts or mixtures thereof.
グリシジル基を含有するエチレン性不飽和基を有する化合物としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられる。なかでも、付加反応の反応性、重合安定性、光硬化性の点から、グリシジルメタクリレートが好ましい。これらのグリシジル基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Examples of the compound having an ethylenically unsaturated group containing a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl. And methacrylate. Of these, glycidyl methacrylate is preferable from the viewpoint of the reactivity of the addition reaction, polymerization stability, and photocurability. These compounds having an ethylenically unsaturated group containing a glycidyl group can be used alone or in combination.
（Ｄ）グリシジル基を含有するエチレン性不飽和単量体と付加反応可能なエチレン性不飽和基を有する化合物としては、カルボキシル基を含有するエチレン性不飽和基を有する化合物が挙げられる。 (D) As a compound which has an ethylenically unsaturated group which can be addition-reacted with the ethylenically unsaturated monomer containing a glycidyl group, the compound which has an ethylenically unsaturated group containing a carboxyl group is mentioned.
グリシジル基を含有するエチレン性不飽和単量体としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられる。なかでも、付加反応の反応性、重合安定性、光硬化性の点から、グリシジルメタクリレートが好ましい。これらのグリシジル基を含有するエチレン性不飽和単量体は単独であるいは組み合わせて使用することができる。 Examples of the ethylenically unsaturated monomer containing a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Etc. Of these, glycidyl methacrylate is preferable from the viewpoint of the reactivity of the addition reaction, polymerization stability, and photocurability. These ethylenically unsaturated monomers containing a glycidyl group can be used alone or in combination.
カルボキシル基を含有するエチレン性不飽和基を有する化合物としては、アクリル酸、メタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、２−メチルマレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、テトラヒドロフタル酸無水物、それらの金属塩、アンモニウム塩或いはそれらの混合物を挙げられる。なかでも、光硬化性樹脂組成物の貯蔵安定性、付加反応の反応性、重合安定性、光硬化性の点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましい。これらのカルボキシル基を含有するエチレン性不飽和基を有する化合物は単独であるいは組み合わせて使用することができる。 Compounds having an ethylenically unsaturated group containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid , Tetrahydrophthalic anhydride, their metal salts, ammonium salts or mixtures thereof. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred from the viewpoints of storage stability of the photocurable resin composition, reactivity of addition reaction, polymerization stability, and photocurability. These compounds having an ethylenically unsaturated group containing a carboxyl group can be used alone or in combination.
通常、これらの付加反応は、一般に用いられる周知の触媒存在下に加熱することで容易に行うことができる。 Usually, these addition reactions can be easily carried out by heating in the presence of a commonly used catalyst.
転相により水系媒体に分散させる重合体に反応性官能基を導入するために用いられる、官能基を含有するエチレン性不飽和単量体は、重合に用いられる全てのエチレン性不飽和単量体１００質量部に対して、５〜５０質量部使用することが好ましい。５質量部より少ないと、付加反応させるエチレン性不飽和基を有する化合物が減少し、光硬化性が充分でなくなり、５０質量部より多いと重合中にゲル化する傾向にある。 The ethylenically unsaturated monomer containing a functional group used to introduce a reactive functional group into a polymer dispersed in an aqueous medium by phase inversion is all ethylenically unsaturated monomers used for polymerization. It is preferable to use 5 to 50 parts by mass with respect to 100 parts by mass. When the amount is less than 5 parts by mass, the compound having an ethylenically unsaturated group to be subjected to addition reaction is decreased, and the photocurability is not sufficient. When the amount is more than 50 parts by mass, gelation tends to occur during polymerization.
転相により水系媒体に分散させる重合体の反応性官能基に付加反応させるエチレン性不飽和基を有する化合物は、固形分で重合体１００質量部に対して、５〜５０質量部を使用することが好ましい。５質量部より少ないと、光硬化性が充分でなく、５０質量部より多いと付加反応中にゲル化する傾向にある。 The compound having an ethylenically unsaturated group to be added to the reactive functional group of the polymer dispersed in the aqueous medium by phase inversion should be used in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the polymer. Is preferred. If it is less than 5 parts by mass, the photocurability is not sufficient, and if it is more than 50 parts by mass, it tends to gel during the addition reaction.
本発明において、カルボキシル基の中和に用いられる塩基としては、特に代表的なもののみを例示するに止めれば、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、トリエタノールアミン、トリエチルアミン、トリメチルアミン、ジエタノールアミン、ジメチルアミノエチルメタクリレート、ジメチルアミノプロピルメタクリレート、トリアリルアミン等が挙げられる。塩基の使用範囲としては、カルボキシル基に対して、０．５〜１．５当量が望ましい。０．５当量より少ないと水への分散安定性が低下し、１．５当量より多いと硬化後の皮膜としての耐水性が低下する。 In the present invention, as the base used for neutralizing the carboxyl group, only typical ones can be exemplified. For example, sodium hydroxide, potassium hydroxide, ammonia, triethanolamine, triethylamine, trimethylamine, diethanolamine Dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, triallylamine and the like. As a use range of a base, 0.5-1.5 equivalent is desirable with respect to a carboxyl group. When the amount is less than 0.5 equivalent, the dispersion stability in water is lowered, and when the amount is more than 1.5 equivalent, the water resistance as a film after curing is lowered.
なお、本発明で用いられた水系媒体とは、水が７０質量％以上のものを意味し、３０質量％未満であれば、水溶性の有機溶媒を含んでいてもよい。水溶性の有機溶媒としては、メタノール、エタノール、イソプロパノール、メチルエチルケトン等を挙げることができ、これらは単独であるいは二つ以上を組み合わせて使用することができる。 The aqueous medium used in the present invention means that the water content is 70% by mass or more, and may contain a water-soluble organic solvent as long as it is less than 30% by mass. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, methyl ethyl ketone and the like, and these can be used alone or in combination of two or more.
本発明の水系媒体に分散した光硬化組成物には、上記で説明した成分の他、必要に応じて他の樹脂、光重合促進剤、重合禁止剤、成膜助剤、可塑剤、防腐剤、消泡剤、界面活性剤等の公知慣用の添加剤を、本発明の目的を損なわない範囲で便宜選択して添加することも可能である。 In addition to the components described above, the photocurable composition dispersed in the aqueous medium of the present invention includes other resins, photopolymerization accelerators, polymerization inhibitors, film forming aids, plasticizers, and preservatives as necessary. In addition, well-known and commonly used additives such as antifoaming agents and surfactants can be conveniently selected and added within a range not impairing the object of the present invention.
以下、実施例を挙げて、本発明を具体的に説明する。なお、以下において、部は質量部を意味する。 Hereinafter, the present invention will be specifically described with reference to examples. In the following, “part” means “part by mass”.
（試験片の作製）
ポリＭＭＡ板に膜厚が５μｍもしくは５０μｍとなるよう、アプリケーターで塗布し、６０℃、１０分で乾燥させた。ＵＶ照射器（ウシオ電機株式会社製 超高圧水銀ランプＵＳＨ−２５０ＳＣ）にて、積算照度５００ｍＪ／ｃｍ２になるよう紫外線照射して硬化させ、以下の試験にて評価を行った。
(Preparation of test piece)
The polyMMA plate was coated with an applicator so that the film thickness was 5 μm or 50 μm, and dried at 60 ° C. for 10 minutes. Using a UV irradiator (Ushio Electric Co., Ltd., ultra-high pressure mercury lamp USH-250SC), it was cured by irradiating with ultraviolet rays so as to have an integrated illuminance of 500 mJ / cm 2, and evaluated by the following tests.
（鉛筆硬度）
ポリＭＭＡ板に塗装した硬化塗膜にて、ＪＩＳ−Ｋ−５４００に基づいて測定した。
(Pencil hardness)
It measured based on JIS-K-5400 in the cured coating film applied to the polyMMA board.
（密着性）
ポリＭＭＡ板に塗装した硬化塗膜にクロスカットを入れ、カットした塗膜上にセロテープ（登録商標）を貼った。１時間放置後、このセロテープ（登録商標）を剥離して密着性を評価した。評価基準は以下のように行った。
○：全く剥離無し △：一部分が剥離する ×：全面剥離する
(Adhesion)
A cross cut was put into the cured coating film coated on the polyMMA plate, and cellotape (registered trademark) was pasted on the cut coating film. After leaving for 1 hour, this cello tape (registered trademark) was peeled off to evaluate the adhesion. The evaluation criteria were as follows.
○: No peeling Δ: Partial peeling ×: Full peeling
（耐温水性）
ポリＭＭＡ板に塗装した硬化塗膜を６０℃の温水に１週間浸漬した。評価基準は以下のように行った。
○：変化無し △：一部白化 ×：全面白化
(Hot water resistance)
The cured coating film coated on the polyMMA plate was immersed in 60 ° C. warm water for 1 week. The evaluation criteria were as follows.
○: No change △: Partially whitened ×: Fully whitened
（液安定性）
水系媒体に分散した光硬化性樹脂組成物を４０℃下に１週間放置した後、液の状態を確認した。また、後添加したものは、光重合開始剤直後の混和状態を確認した。評価基準は以下のように行った。
○：変化無し ×：ゲル化
(Liquid stability)
The photocurable resin composition dispersed in the aqueous medium was allowed to stand at 40 ° C. for 1 week, and then the state of the liquid was confirmed. Moreover, what was added later confirmed the mixing state immediately after a photoinitiator. The evaluation criteria were as follows.
○: No change ×: Gelation
（実施例１）
温度計、撹拌棒、還流冷却器、及び、滴下漏斗を備えた遮光性反応容器に、イオン交換水を１２０部仕込み８０℃まで昇温した。一方、イオン交換水２９１部およびアニオン性界面活性剤ニューレックスＲ（日本油脂株式会社製 ノルマルドデシルベンゼンスルホン酸ナトリウム）４８部、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン４５部を溶解したスチレン１９８部、２−エチルヘキシルアクリレート９７部、メタクリル酸６５部をホモミキサーで乳化し、混合乳化液をつくった。上記の容器中に、過硫酸カリウム０．５部、無水重亜硫酸ソーダ０．４部を仕込み、乳化重合を開始した。重合は混合乳化液と過硫酸カリウム０．５部をイオン交換水３０部で溶解した過硫酸カリウム水溶液及び無水重亜硫酸ソーダ０．４部をイオン交換水３０部で溶解した無水重亜硫酸ソーダ水溶液をそれぞれ３時間かけて滴下して行った。この間、容器内は８０℃に保った。滴下終了後、５時間、８０℃に保ち、熟成を行った。メトキノン０．５部を添加し、グリシジルメタクリレート９０部を添加し、８０℃、３時間保持し、重合体にエチレン性不飽和基を付加した。得られた水系媒体に分散した光硬化性樹脂組成物は、不揮発分４５％であり、テストを行い、表１の結果を得た。
Example 1
In a light-shielding reaction vessel equipped with a thermometer, a stirring bar, a reflux condenser, and a dropping funnel, 120 parts of ion-exchanged water was charged and heated to 80 ° C. On the other hand, 291 parts of ion-exchanged water and 48 parts of anionic surfactant Newrex R (sodium normal dodecylbenzenesulfonate manufactured by NOF Corporation), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholine 198 parts of styrene, 45 parts of 2-ethylhexyl acrylate and 65 parts of methacrylic acid in which 45 parts of nopropan-1-one were dissolved were emulsified with a homomixer to prepare a mixed emulsion. In the container, 0.5 part of potassium persulfate and 0.4 part of anhydrous sodium bisulfite were charged, and emulsion polymerization was started. The polymerization was carried out by mixing a mixed emulsion and an aqueous potassium persulfate solution in which 0.5 part of potassium persulfate was dissolved in 30 parts of ion-exchanged water and an anhydrous sodium bisulfite solution in which 0.4 part of anhydrous sodium bisulfite was dissolved in 30 parts of ion-exchanged water. Each was dropped over 3 hours. During this time, the inside of the container was kept at 80 ° C. After completion of the dropping, the mixture was kept at 80 ° C. for 5 hours for aging. 0.5 parts of methoquinone was added, 90 parts of glycidyl methacrylate was added, and maintained at 80 ° C. for 3 hours to add an ethylenically unsaturated group to the polymer. The obtained photocurable resin composition dispersed in the aqueous medium had a non-volatile content of 45%, was tested, and the results shown in Table 1 were obtained.
（実施例２）
実施例２として、実施例１における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンに変更した以外はすべて実施例１と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表１に示す。
(Example 2)
As Example 2, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 1 was replaced with 1- [4- (2-hydroxyethoxy) -phenyl] -2. Except for changing to -hydroxy-2-methyl-1-propan-1-one, the same operation as in Example 1 was performed to obtain a photocurable resin composition dispersed in an aqueous medium. The results are shown in Table 1.
（実施例３）
実施例３として、温度計、撹拌棒、還流冷却器、及び、滴下漏斗を備えた遮光性反応容器に、イオン交換水を１２０部仕込み８０℃まで昇温した。一方、イオン交換水２９１部およびアニオン性界面活性剤ニューレックスＲ（日本油脂株式会社製 ノルマルドデシルベンゼンスルホン酸ナトリウム）４８部、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン４５部を溶解したスチレン１９８部、２−エチルヘキシルアクリレート９７部、グリシジルメタクリレート６５部をホモミキサーで乳化し、混合乳化液を作製した。上記の容器中に、過硫酸カリウム０．５部、無水重亜硫酸ソーダ０．４部を仕込み、乳化重合を開始した。重合は混合乳化液と過硫酸カリウム０．５部をイオン交換水３０部で溶解した過硫酸カリウム水溶液及び無水重亜硫酸ソーダ０．４部をイオン交換水３０部で溶解した無水重亜硫酸ソーダ水溶液をそれぞれ３時間かけて滴下して行った。この間容器内は８０℃に保った。滴下終了後、５時間、８０℃に保ち、熟成を行った。メトキノン０．５部を添加し、アクリル酸９０部を添加し、８０℃、３時間保持し、重合体にエチレン性不飽和基を付加した。得られた水系媒体に分散した光硬化性樹脂組成物は、不揮発分４５％であり、テストを行い、表１の結果を得た。
(Example 3)
As Example 3, 120 parts of ion-exchanged water was charged into a light-shielding reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel and heated to 80 ° C. On the other hand, 291 parts of ion-exchanged water and 48 parts of anionic surfactant Newrex R (sodium normal dodecylbenzenesulfonate manufactured by NOF Corporation), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholine 198 parts of styrene, 45 parts of 2-ethylhexyl acrylate and 65 parts of glycidyl methacrylate in which 45 parts of nopropan-1-one were dissolved were emulsified with a homomixer to prepare a mixed emulsion. In the container, 0.5 part of potassium persulfate and 0.4 part of anhydrous sodium bisulfite were charged, and emulsion polymerization was started. The polymerization was carried out by mixing a mixed emulsion and an aqueous potassium persulfate solution in which 0.5 part of potassium persulfate was dissolved in 30 parts of ion-exchanged water and an anhydrous sodium bisulfite solution in which 0.4 part of anhydrous sodium bisulfite was dissolved in 30 parts of ion-exchanged water. Each was dropped over 3 hours. During this time, the inside of the container was kept at 80 ° C. After completion of the dropping, the mixture was kept at 80 ° C. for 5 hours for aging. 0.5 parts of methoquinone was added, 90 parts of acrylic acid was added, kept at 80 ° C. for 3 hours, and an ethylenically unsaturated group was added to the polymer. The obtained photocurable resin composition dispersed in the aqueous medium had a non-volatile content of 45%, was tested, and the results shown in Table 1 were obtained.
（実施例４）
実施例４として、実施例３における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンに変更した以外はすべて実施例３と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表１に示す。
Example 4
As Example 4, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 3 was replaced with 1- [4- (2-hydroxyethoxy) -phenyl] -2. Except for changing to -hydroxy-2-methyl-1-propan-1-one, the same operation as in Example 3 was performed to obtain a photocurable resin composition dispersed in an aqueous medium. The results are shown in Table 1.
（実施例５）
実施例５として、実施例１における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１３５部に変更した以外はすべて実施例１と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表１に示す。
(Example 5)
As Example 5, the same operation as in Example 1 was performed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 1 was changed to 135 parts. And a photocurable resin composition dispersed in an aqueous medium was obtained. The results are shown in Table 1.
（実施例６）
実施例６として、実施例１における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１８０部に変更した以外はすべて実施例１と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表１に示す。
(Example 6)
As Example 6, the same operation as in Example 1 was performed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 1 was changed to 180 parts. And a photocurable resin composition dispersed in an aqueous medium was obtained. The results are shown in Table 1.
（比較例１）
比較例１として、実施例１における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表２に示す。
(Comparative Example 1)
As Comparative Example 1, emulsion polymerization was performed without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 1 in an ethylenically unsaturated monomer. And a resin composition was obtained, and the same operation was performed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and added later. However, the solution gelled immediately after the addition and the test was stopped. The results are shown in Table 2.
（比較例２）
比較例２として、実施例２における１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表２に示す。
(Comparative Example 2)
As Comparative Example 2, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one in Example 2 was dissolved in an ethylenically unsaturated monomer. Without conducting emulsion polymerization to obtain a resin composition, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is dissolved in methyl ethyl ketone, The same operation was performed except that it was added after the addition, but the liquid gelled immediately after the addition and the test was stopped. The results are shown in Table 2.
（比較例３）
比較例３として、実施例３における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表２に示す。
(Comparative Example 3)
As Comparative Example 3, emulsion polymerization was performed without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 3 in an ethylenically unsaturated monomer. And a resin composition was obtained, and the same operation was performed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and added later. However, the solution gelled immediately after the addition and the test was stopped. The results are shown in Table 2.
（比較例４）
比較例４として、実施例４における１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表２に示す。
(Comparative Example 4)
As Comparative Example 4, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one in Example 4 was dissolved in an ethylenically unsaturated monomer. Without conducting emulsion polymerization to obtain a resin composition, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is dissolved in methyl ethyl ketone, The same operation was performed except that it was added after the addition, but the liquid gelled immediately after the addition and the test was stopped. The results are shown in Table 2.
（比較例５）
比較例５として、実施例１における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン２２．５部をメチルエチルケトンに溶解し、後添加し、樹脂組成物を得た。結果を表２に示す。
(Comparative Example 5)
As Comparative Example 5, emulsion polymerization was performed without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 1 in an ethylenically unsaturated monomer. And 22.5 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one is dissolved in methyl ethyl ketone and added afterwards to obtain a resin composition. Obtained. The results are shown in Table 2.
表１及び２の結果から、光重合開始剤を乳化重合の際にあらかじめ添加することにより、光重合開始剤を乳化重合した後に添加する場合に比べ、光重合開始剤を多量に添加することが可能となり、その結果、膜厚５μｍ、５０μｍのいずれにおいても、塗装後に光硬化させたときの硬度、密着性及び耐温水性のすべてに優れた樹脂組成物が得られることがわかる。 From the results of Tables 1 and 2, it is possible to add a large amount of photopolymerization initiator by adding the photopolymerization initiator in advance during emulsion polymerization, compared to the case where the photopolymerization initiator is added after emulsion polymerization. As a result, it can be seen that a resin composition excellent in all of hardness, adhesion, and hot water resistance when photocured after coating is obtained at a film thickness of 5 μm or 50 μm.
（実施例７）
温度計、撹拌棒、還流冷却器、及び、滴下漏斗を備えた遮光性反応容器に、メチルエチルケトン３０部を入れて攪拌、８０℃に加熱し、メチルメタクリレート１１４部、２−エチルヘキシルアクリレート２１部、２−ヒドロキシエチルメタクリレート５部、アクリル酸１１部、アゾビスイソブチロニトリル５部、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン３０部を２時間にわたって滴下した。滴下終了後さらに８０℃で５時間攪拌した。その後、メトキノン０．５部、及び、ジペンタエリスリトールヘキサアクリレート１５０部を添加し、１５分撹拌し、均一化させた。その後、アンモニア水７部添加し、中和させ、イオン交換水７００部を３０分間にわたって滴下した。得られた水系媒体に分散した光硬化性樹脂組成物は、不揮発分３０％であり、テストを行い、表３の結果を得た。
(Example 7)
In a light-shielding reaction vessel equipped with a thermometer, stirring bar, reflux condenser, and dropping funnel, 30 parts of methyl ethyl ketone was stirred and heated to 80 ° C., and 114 parts of methyl methacrylate, 21 parts of 2-ethylhexyl acrylate, 2 parts, -5 parts of hydroxyethyl methacrylate, 11 parts of acrylic acid, 5 parts of azobisisobutyronitrile, 30 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one for 2 hours Dripped over. After completion of dropping, the mixture was further stirred at 80 ° C. for 5 hours. Thereafter, 0.5 part of methoquinone and 150 parts of dipentaerythritol hexaacrylate were added and stirred for 15 minutes to make uniform. Thereafter, 7 parts of ammonia water was added to neutralize, and 700 parts of ion exchange water was added dropwise over 30 minutes. The obtained photocurable resin composition dispersed in the aqueous medium had a nonvolatile content of 30%, was tested, and the results shown in Table 3 were obtained.
（実施例８）
実施例８として、実施例７における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンに変更した以外はすべて実施例７と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表３に示す。
(Example 8)
As Example 8, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 7 was replaced with 1- [4- (2-hydroxyethoxy) -phenyl] -2. Except for changing to -hydroxy-2-methyl-1-propan-1-one, the same operation as in Example 7 was performed to obtain a photocurable resin composition dispersed in an aqueous medium. The results are shown in Table 3.
（実施例９）
温度計、撹拌棒、還流冷却器、及び、滴下漏斗を備えた遮光性反応容器に、メチルエチルケトン３０部を入れて攪拌、８０℃に加熱し、メチルメタクリレート１１４部、２−エチルヘキシルアクリレート２１部、２−ヒドロキシエチルメタクリレート５部、アクリル酸１１部、アゾビスイソブチロニトリル５部、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン３０部を２時間にわたって滴下した。滴下終了後さらに８０℃で５時間攪拌した。その後、メトキノン０．５部、を及び、ジペンタエリスリトールヘキサアクリレート１５０部を添加し、１５分撹拌し、均一化させた。その後、アンモニア水７部添加し、中和させ、イオン交換水７００部を３０分間にわたって滴下した。更に、グリシジルメタクリレート１０部を３０分間にわたって滴下し、重合体にエチレン性不飽和基を付加反応した。得られた水系媒体に分散した光硬化性樹脂組成物は、不揮発分３０％であり、テストを行い、表３の結果を得た。
Example 9
In a light-shielding reaction vessel equipped with a thermometer, stirring bar, reflux condenser, and dropping funnel, 30 parts of methyl ethyl ketone was stirred and heated to 80 ° C., and 114 parts of methyl methacrylate, 21 parts of 2-ethylhexyl acrylate, 2 parts, -5 parts of hydroxyethyl methacrylate, 11 parts of acrylic acid, 5 parts of azobisisobutyronitrile, 30 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one for 2 hours Dripped over. After completion of dropping, the mixture was further stirred at 80 ° C. for 5 hours. Thereafter, 0.5 part of methoquinone and 150 parts of dipentaerythritol hexaacrylate were added and stirred for 15 minutes to make uniform. Thereafter, 7 parts of ammonia water was added to neutralize, and 700 parts of ion exchange water was added dropwise over 30 minutes. Further, 10 parts of glycidyl methacrylate was added dropwise over 30 minutes, and an ethylenically unsaturated group was added to the polymer. The obtained photocurable resin composition dispersed in the aqueous medium had a nonvolatile content of 30%, was tested, and the results shown in Table 3 were obtained.
（実施例１０）
実施例１０として、実施例９における２−ヒドロキシエチルメタクリレート５部を１５部にし、グリシジルメタクリレートを２−イソシアナートエチルアクリレートに変更した以外はすべて実施例９と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表３に示す。
(Example 10)
As Example 10, except that 5 parts of 2-hydroxyethyl methacrylate in Example 9 was changed to 15 parts and glycidyl methacrylate was changed to 2-isocyanatoethyl acrylate, all the same operations as in Example 9 were performed, and dispersed in an aqueous medium. The obtained photocurable resin composition was obtained. The results are shown in Table 3.
（実施例１１）
実施例１１として、実施例７における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを９０部に変更した以外はすべて実施例７と同様の操作を行い、水系媒体に分散した光硬化性樹脂組成物を得た。結果を表３に示す。
(Example 11)
As Example 11, the same operation as in Example 7 was performed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 7 was changed to 90 parts. And a photocurable resin composition dispersed in an aqueous medium was obtained. The results are shown in Table 3.
（実施例１２）
実施例１２として、実施例７における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンを１２０部に変更した以外はすべて実施例７と同様の操作を行い、樹脂組成物を得た。結果を表３に示す。
(Example 12)
As Example 12, all operations were the same as Example 7 except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 7 was changed to 120 parts. And a resin composition was obtained. The results are shown in Table 3.
（比較例６）
比較例６として、実施例７における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表４に示す。
(Comparative Example 6)
As Comparative Example 6, a resin composition was prepared without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 7 in an ethylenically unsaturated monomer. The same procedure was followed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and added later. Gelation occurred immediately after addition and the test was stopped. The results are shown in Table 4.
（比較例７）
比較例７として、実施例８における１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをエチレン性不飽和単量体に溶解せずに、樹脂組成物を得、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表４に示す。
(Comparative Example 7)
As Comparative Example 7, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one in Example 8 was dissolved in an ethylenically unsaturated monomer. 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one was dissolved in methyl ethyl ketone and added afterwards. The same operation was carried out, but the liquid gelled immediately after the addition and the test was stopped. The results are shown in Table 4.
（比較例８）
比較例８として、実施例９における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表４に示す。
(Comparative Example 8)
As Comparative Example 8, the resin composition was obtained without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 9 in the ethylenically unsaturated monomer. The same procedure was followed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and added later. Gelation occurred immediately after addition and the test was stopped. The results are shown in Table 4.
（比較例９）
比較例９として、実施例１０における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをメチルエチルケトンに溶解し、後添加する以外は、同様の操作を行ったが、液が後添加直後にゲル化し、テストを中止した。結果を表４に示す。
(Comparative Example 9)
As Comparative Example 9, a resin composition was prepared without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 10 in an ethylenically unsaturated monomer. The same procedure was followed except that 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and added later. Gelation occurred immediately after addition and the test was stopped. The results are shown in Table 4.
（比較例１０）
比較例１０として、実施例７における２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オンをエチレン性不飽和単量体に溶解せずに、乳化重合を行い、樹脂組成物を得、２−メチル−１［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン１５部をメチルエチルケトンに溶解し、後添加し、樹脂組成物を得た。結果を表４に示す。
(Comparative Example 10)
As Comparative Example 10, emulsion polymerization was performed without dissolving 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one in Example 7 in an ethylenically unsaturated monomer. To obtain a resin composition, and 15 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one was dissolved in methyl ethyl ketone and then added to obtain a resin composition. . The results are shown in Table 4.
表３及び４の結果から、光重合開始剤を重合の際にあらかじめ添加することにより、光重合開始剤を重合後に添加する場合に比べ、光重合開始剤を多量に添加することが可能となり、その結果、膜厚５μｍ、５０μｍのいずれにおいても、塗装後に光硬化させたときの硬度、密着性及び耐温水性のすべてに優れた樹脂組成物が得られることがわかる。 From the results of Tables 3 and 4, by adding the photopolymerization initiator in advance during polymerization, it becomes possible to add a large amount of photopolymerization initiator as compared with the case where the photopolymerization initiator is added after polymerization, As a result, it can be seen that a resin composition excellent in all of hardness, adhesion, and hot water resistance when photocured after coating is obtained at a film thickness of 5 μm or 50 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014091792A (en) * | 2012-11-05 | 2014-05-19 | Negami Kogyo Kk | Method for producing reactive acrylic resin |
| WO2018131682A1 (en) * | 2017-01-13 | 2018-07-19 | 日産化学工業株式会社 | Cured film forming composition, alignment material and retardation material |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56114941A (en) * | 1980-02-15 | 1981-09-09 | Nippon Paint Co Ltd | Photosensitive resin composition |
| JPS63206745A (en) * | 1987-02-23 | 1988-08-26 | Ube Ind Ltd | Formation of photographically developable photoresist |
| JPH0478856A (en) * | 1990-07-20 | 1992-03-12 | Toagosei Chem Ind Co Ltd | Method for stabilizing emulsion type electrodeposition bath for forming photoresist film |
| JPH0627649A (en) * | 1992-07-06 | 1994-02-04 | Oji Kako Kk | Color photographic photosensitive resin composition |
| JPH07292012A (en) * | 1994-04-25 | 1995-11-07 | W R Grace & Co | Preparation of photosensitive resin composition |
| JPH09157495A (en) * | 1995-12-02 | 1997-06-17 | Arakawa Chem Ind Co Ltd | Emulsion curable with active energy ray and its production |
| JPH10195372A (en) * | 1997-01-08 | 1998-07-28 | Toagosei Co Ltd | Water-base active-energy-ray-curable coating composition for metal |
| JP2002202600A (en) * | 2000-12-27 | 2002-07-19 | Toyo Gosei Kogyo Kk | Photosensitive composition for metal or metal oxide etching |
| JP2005002276A (en) * | 2003-06-13 | 2005-01-06 | Kao Corp | Photosetting water-based resin composition |
| JP2005179400A (en) * | 2003-12-16 | 2005-07-07 | Mitsui Takeda Chemicals Inc | AQUEOUS DISPERSION, ITS PREPARATION METHOD AND METHOD FOR BONDING MOLDED PRODUCT COMPRISING ETHYLENE-alpha-OLEFIN COPOLYMER |
| WO2009063955A1 (en) * | 2007-11-16 | 2009-05-22 | Fujifilm Corporation | Radiation-sensitive resin composition for forming spacer, spacer, method for forming spacer, and liquid crystal display device |
| JP2010518055A (en) * | 2007-02-08 | 2010-05-27 | ヘクシス | Method for antibacterial protection of object surface using antibacterial self-adhesive plastic film |
-
2009
- 2009-06-24 JP JP2009150343A patent/JP5552266B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56114941A (en) * | 1980-02-15 | 1981-09-09 | Nippon Paint Co Ltd | Photosensitive resin composition |
| JPS63206745A (en) * | 1987-02-23 | 1988-08-26 | Ube Ind Ltd | Formation of photographically developable photoresist |
| JPH0478856A (en) * | 1990-07-20 | 1992-03-12 | Toagosei Chem Ind Co Ltd | Method for stabilizing emulsion type electrodeposition bath for forming photoresist film |
| JPH0627649A (en) * | 1992-07-06 | 1994-02-04 | Oji Kako Kk | Color photographic photosensitive resin composition |
| JPH07292012A (en) * | 1994-04-25 | 1995-11-07 | W R Grace & Co | Preparation of photosensitive resin composition |
| JPH09157495A (en) * | 1995-12-02 | 1997-06-17 | Arakawa Chem Ind Co Ltd | Emulsion curable with active energy ray and its production |
| JPH10195372A (en) * | 1997-01-08 | 1998-07-28 | Toagosei Co Ltd | Water-base active-energy-ray-curable coating composition for metal |
| JP2002202600A (en) * | 2000-12-27 | 2002-07-19 | Toyo Gosei Kogyo Kk | Photosensitive composition for metal or metal oxide etching |
| JP2005002276A (en) * | 2003-06-13 | 2005-01-06 | Kao Corp | Photosetting water-based resin composition |
| JP2005179400A (en) * | 2003-12-16 | 2005-07-07 | Mitsui Takeda Chemicals Inc | AQUEOUS DISPERSION, ITS PREPARATION METHOD AND METHOD FOR BONDING MOLDED PRODUCT COMPRISING ETHYLENE-alpha-OLEFIN COPOLYMER |
| JP2010518055A (en) * | 2007-02-08 | 2010-05-27 | ヘクシス | Method for antibacterial protection of object surface using antibacterial self-adhesive plastic film |
| WO2009063955A1 (en) * | 2007-11-16 | 2009-05-22 | Fujifilm Corporation | Radiation-sensitive resin composition for forming spacer, spacer, method for forming spacer, and liquid crystal display device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014091792A (en) * | 2012-11-05 | 2014-05-19 | Negami Kogyo Kk | Method for producing reactive acrylic resin |
| WO2018131682A1 (en) * | 2017-01-13 | 2018-07-19 | 日産化学工業株式会社 | Cured film forming composition, alignment material and retardation material |
| JPWO2018131682A1 (en) * | 2017-01-13 | 2019-11-07 | 日産化学株式会社 | Cured film forming composition, alignment material and retardation material |
| JP7070839B2 (en) | 2017-01-13 | 2022-05-18 | 日産化学株式会社 | Hardened film forming composition, alignment material and retardation material |
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