JP5495087B2 - Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same - Google Patents
Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same Download PDFInfo
- Publication number
- JP5495087B2 JP5495087B2 JP2013546113A JP2013546113A JP5495087B2 JP 5495087 B2 JP5495087 B2 JP 5495087B2 JP 2013546113 A JP2013546113 A JP 2013546113A JP 2013546113 A JP2013546113 A JP 2013546113A JP 5495087 B2 JP5495087 B2 JP 5495087B2
- Authority
- JP
- Japan
- Prior art keywords
- active energy
- energy ray
- curable composition
- mass
- curable
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 52
- 238000007639 printing Methods 0.000 title claims description 46
- 239000011248 coating agent Substances 0.000 title description 45
- 238000000576 coating method Methods 0.000 title description 45
- 125000003118 aryl group Chemical group 0.000 claims description 53
- 239000003822 epoxy resin Substances 0.000 claims description 48
- 229920000647 polyepoxide Polymers 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 24
- -1 ethylene oxide-modified trimethylolpropane triacrylate Chemical class 0.000 claims description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008199 coating composition Substances 0.000 claims 1
- 239000000976 ink Substances 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 239000004593 Epoxy Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 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 13
- 238000000034 method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000003595 mist Substances 0.000 description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000003504 photosensitizing agent Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000002649 leather substitute Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- MLKGHQNOKUCQBA-UHFFFAOYSA-N (2-methyl-4-phenylphenyl)-phenylmethanone Chemical compound CC1=CC(C=2C=CC=CC=2)=CC=C1C(=O)C1=CC=CC=C1 MLKGHQNOKUCQBA-UHFFFAOYSA-N 0.000 description 1
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- WNLFUMVKGWEXBI-UHFFFAOYSA-N 2-chloro-10h-acridin-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3NC2=C1 WNLFUMVKGWEXBI-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RYDOQJPDRXMRRP-UHFFFAOYSA-N 2-methylpropan-1-one Chemical compound CC(C)[C]=O RYDOQJPDRXMRRP-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- NJVHCUNZAMFQNA-UHFFFAOYSA-N azane;n-hydroxy-n-phenylnitrous amide Chemical compound N.O=NN(O)C1=CC=CC=C1 NJVHCUNZAMFQNA-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007598 dipping method Methods 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 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
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 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
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
Description
塗料、インキ等の原料として有用な活性エネルギー線硬化性組成物に関する。さらには、該組成物を用いた活性エネルギー線硬化性塗料及び活性エネルギー線硬化性印刷インキに関する。 The present invention relates to an active energy ray-curable composition useful as a raw material for paints, inks and the like. Furthermore, the present invention relates to an active energy ray curable coating and an active energy ray curable printing ink using the composition.
活性エネルギー線硬化性組成物は、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、携帯電話等の各種プラスチック基材用ハードコート剤、紙等のオーバーコート剤、印刷インキ用バインダー、ソルダーレジスト等の様々な分野で使用されている。中でもエポキシ樹脂に、アクリル酸又はメタクリル酸を付加したエポキシアクリレート樹脂は、基材への密着性、接着性に優れる材料として、様々な分野において多用されてきた（例えば、特許文献１参照。）。 Active energy ray-curable composition has a low heat history on the coated substrate and is excellent in coating film hardness and scratch resistance. For example, hard coating agents for various plastic substrates such as home appliances and mobile phones, paper, etc. It is used in various fields such as overcoat agent, binder for printing ink, solder resist. Among them, an epoxy acrylate resin obtained by adding acrylic acid or methacrylic acid to an epoxy resin has been widely used in various fields as a material excellent in adhesion and adhesion to a base material (for example, see Patent Document 1).
しかしながら、従来のエポキシアクリレート樹脂を、例えば、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用いた場合には、スマートフォンのタッチパネルようにハードコートの表面を指で擦る機会が増加するために、その表面により高い耐擦傷性が必要となってきた。また、エポキシアクリレート樹脂を印刷インキ用バインダーとして用いる場合には、印刷インキに必要な乳化適性が乏しかったり、印刷インキの耐ミスチング性が劣ったりする問題があった。この問題を解決するために、ロジン系樹脂、ジアリルフタレート樹脂等の印刷適性に優れる樹脂を併用する手法があるが（例えば、特許文献２参照。）、この併用でも、印刷インキのポリプロピレンやナイロンフィルムへの密着性が低下したり、活性エネルギー線による硬化性が低下したりする問題があった。 However, when a conventional epoxy acrylate resin is used, for example, as a hard coat agent for plastic substrates of home appliances, mobile phones, etc., the chance of rubbing the surface of the hard coat with a finger like a smartphone touch panel increases. In addition, higher scratch resistance is required on the surface. In addition, when an epoxy acrylate resin is used as a binder for printing ink, there are problems that the emulsification suitability required for the printing ink is poor and the misting resistance of the printing ink is poor. In order to solve this problem, there is a method of using a resin having excellent printability such as rosin resin and diallyl phthalate resin (see, for example, Patent Document 2). Even in this combination, polypropylene or nylon film of printing ink is used. There was a problem that the adhesiveness to the surface was lowered or the curability by the active energy ray was lowered.
そこで、ハードコート剤に用いた場合には、その硬化塗膜に高い耐擦傷性を付与でき、印刷インキに用いた場合には、該インキに高い耐ミスチング性を付与でき、その硬化塗膜に基材に対する高い密着性と高い耐溶剤性を付与できる活性エネルギー線硬化性組成物が求められていた。 Therefore, when used in a hard coating agent, high scratch resistance can be imparted to the cured coating film, and when used in printing ink, high misting resistance can be imparted to the ink. There has been a demand for an active energy ray-curable composition that can provide high adhesion to a substrate and high solvent resistance.
本発明が解決しようとする課題は、ハードコート剤等の塗料に用いた場合に優れた耐擦傷性を付与することができ、印刷インキに用いた場合には優れた耐ミスチング性、基材への密着性及び耐溶剤性を付与することのできる活性エネルギー線硬化性組成物を提供することである。また、この活性エネルギー線硬化性組成物を用いた活性エネルギー線硬化性塗料及び活性エネルギー線硬化性印刷インキを提供することである。 The problem to be solved by the present invention is that it can impart excellent scratch resistance when used in paints such as hard coat agents, and has excellent misting resistance when used in printing ink. It is providing the active energy ray-curable composition which can provide adhesiveness and solvent resistance. Moreover, it is providing the active energy ray-curable coating material and active energy ray-curable printing ink using this active energy ray-curable composition.
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、トリフェニルホスフィン存在下、特定の多官能アクリレートと、芳香族ジカルボン酸と、芳香族エポキシ樹脂とを特定の比率で反応させ、次いで、得られた反応物に、重合性不飽和基を有するカルボン酸を反応させることにより得られる活性エネルギー線硬化性組成物は、ハードコート剤等の塗料に用いた場合には、その硬化塗膜に高い耐擦傷性を付与でき、印刷インキに用いた場合には、該インキに高い耐ミスチング性を付与でき、その硬化塗膜に基材に対する高い密着性と高い耐溶剤性を付与できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors reacted a specific polyfunctional acrylate, an aromatic dicarboxylic acid, and an aromatic epoxy resin in a specific ratio in the presence of triphenylphosphine. Then, the active energy ray-curable composition obtained by reacting the resulting reaction product with a carboxylic acid having a polymerizable unsaturated group is cured when used in a paint such as a hard coat agent. High scratch resistance can be imparted to the coating film, and when used in printing ink, high misting resistance can be imparted to the ink, and high adhesion to the substrate and high solvent resistance can be imparted to the cured coating film. The present invention was completed.
すなわち、本発明は、トリフェニルホスフィン存在下、多官能アクリレート（Ａ）と、芳香族ジカルボン酸（Ｂ）と、芳香族エポキシ樹脂（Ｃ）とを反応させ、次いで、得られた反応物に、重合性不飽和基を有するカルボン酸（Ｄ）を反応させることにより得られる活性エネルギー線硬化性組成物であって、前記多官能アクリレート（Ａ）が、トリメチロールプロパントリアクリレート、エチレンオキサイド変性トリメチロールプロパントリアクリレート及びグリセリンプロポキシトリアクリレートからなる群から選ばれる少なくとも１種の多官能アクリレートであり、前記芳香族エポキシ樹脂（Ｃ）の使用量が、前記芳香族ジカルボン酸（Ｂ）が有するカルボキシル基１モルに対して、前記芳香族エポキシ樹脂（Ｃ）が有するエポキシ基が１．１〜３となる範囲であることを特徴とする活性エネルギー線硬化性組成物、該組成物を用いた活性エネルギー線硬化性塗料及び活性エネルギー線硬化性印刷インキに関する。 That is, in the present invention, polyfunctional acrylate (A), aromatic dicarboxylic acid (B), and aromatic epoxy resin (C) are reacted in the presence of triphenylphosphine , and then the obtained reaction product is subjected to An active energy ray-curable composition obtained by reacting a carboxylic acid (D) having a polymerizable unsaturated group , wherein the polyfunctional acrylate (A) is trimethylolpropane triacrylate, ethylene oxide-modified trimethylol It is at least one polyfunctional acrylate selected from the group consisting of propane triacrylate and glycerin propoxy triacrylate, and the amount of the aromatic epoxy resin (C) used is a carboxyl group 1 of the aromatic dicarboxylic acid (B). The epoxy group of the aromatic epoxy resin (C) is The active energy ray curable composition which is a range of a .1～3, to the active energy ray-curable coating and the active energy ray-curable printing ink using the composition.
本発明の活性エネルギー線硬化性組成物は、ハードコート剤等の塗料に用いた場合には、その硬化塗膜に高い耐擦傷性を付与できることから、テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；パソコン、スマートフォン、携帯電話、デジタルカメラ、ゲーム機等の電子機器の筐体；自動車、鉄道車輌等の各種車輌の内装材；化粧板等の各種建材；家具等の木工材料、人工・合成皮革；ＦＲＰ浴槽などの物品の表面に保護膜を形成するハードコート剤の材料として有用である。 The active energy ray-curable composition of the present invention, when used in a paint such as a hard coat agent, can impart high scratch resistance to the cured coating film, so that home appliances such as televisions, refrigerators, washing machines, air conditioners, etc. Housing of products; Housing of electronic devices such as personal computers, smartphones, mobile phones, digital cameras and game machines; Interior materials of various vehicles such as automobiles and railway vehicles; Various building materials such as decorative panels; Woodworking materials such as furniture; Artificial / synthetic leather; useful as a material for hard coat agents that form a protective film on the surface of articles such as FRP bathtubs.
また、本発明の活性エネルギー線硬化性組成物は、印刷インキに用いた場合には、該インキに高い耐ミスチング性を付与でき、その硬化塗膜に基材に対する高い密着性と高い耐溶剤性を付与できることから、平版インキ、グラビアインキ等の各種印刷インキ用のバインダーとして有用である。 In addition, the active energy ray-curable composition of the present invention, when used in printing ink, can impart high misting resistance to the ink, and the cured coating film has high adhesion to the substrate and high solvent resistance. Therefore, it is useful as a binder for various printing inks such as lithographic inks and gravure inks.
本発明の活性エネルギー線硬化型水性樹脂組成物は、トリフェニルホスフィン存在下、多官能アクリレート（Ａ）と、芳香族ジカルボン酸（Ｂ）と、芳香族エポキシ樹脂（Ｃ）とを反応させ、次いで、得られた反応物に、重合性不飽和基を有するカルボン酸（Ｄ）を反応させることにより得られる活性エネルギー線硬化性組成物であって、前記多官能アクリレート（Ａ）が、トリメチロールプロパントリアクリレート、エチレンオキサイド変性トリメチロールプロパントリアクリレート及びグリセリンプロポキシトリアクリレートからなる群から選ばれる少なくとも１種の多官能アクリレートであり、前記芳香族エポキシ樹脂（Ｃ）の使用量が、前記芳香族ジカルボン酸（Ｂ）が有するカルボキシル基１モルに対して、前記芳香族エポキシ樹脂（Ｃ）が有するエポキシ基が１．１〜３となる範囲であるものである。 The active energy ray-curable aqueous resin composition of the present invention reacts the polyfunctional acrylate (A), the aromatic dicarboxylic acid (B), and the aromatic epoxy resin (C) in the presence of triphenylphosphine , An active energy ray-curable composition obtained by reacting the obtained reactant with a carboxylic acid (D) having a polymerizable unsaturated group , wherein the polyfunctional acrylate (A) is trimethylolpropane. It is at least one polyfunctional acrylate selected from the group consisting of triacrylate, ethylene oxide-modified trimethylolpropane triacrylate and glycerin propoxytriacrylate, and the amount of the aromatic epoxy resin (C) used is the aromatic dicarboxylic acid (B) The aromatic epoxy tree for 1 mol of carboxyl group (C) is an epoxy group contained in those ranges to be 1.1 to 3.
前記多官能アクリレート（Ａ）としては、トリメチロールプロパントリアクリレート、エチレンオキサイド変性トリメチロールプロパントリアクリレート及びグリセリンプロポキシトリアクリレートが挙げられる。これらの多官能アクリレート（Ａ）の中でも、エチレンオキサイド変性トリメチロールプロパントリアクリレートが好ましい。また、これらの多官能アクリレート（Ａ）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 is a multifunctional acrylate (A), trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate and glycerol propoxy tri acrylated bets. Among these polyfunctional acrylates (A), ethylene oxide-modified trimethylolpropane triacrylate is preferable. Moreover, these polyfunctional acrylates (A) can be used alone or in combination of two or more.
前記芳香族ジカルボン酸（Ｂ）は、芳香環を有するジカルボン酸である。この芳香族ジカルボン酸（Ｂ）としては、例えば、フタル酸、イソフタル酸、テレフタル酸等が挙げられる。また、芳香族ジカルボン酸（Ｂ）として、無水フタル酸、無水トリメリット酸のような芳香族ジカルボン酸の無水物も用いることができる。これらの芳香族ジカルボン酸（Ｂ）の中でも、前記芳香族エポキシ樹脂が有するエポキシ基との反応性が高いことから、イソフタル酸が好ましい。また、これらの芳香族ジカルボン酸（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。 The aromatic dicarboxylic acid (B) is a dicarboxylic acid having an aromatic ring. Examples of the aromatic dicarboxylic acid (B) include phthalic acid, isophthalic acid, terephthalic acid, and the like. As the aromatic dicarboxylic acid (B), anhydrides of aromatic dicarboxylic acids such as phthalic anhydride and trimellitic anhydride can also be used. Among these aromatic dicarboxylic acids (B), isophthalic acid is preferable because of its high reactivity with the epoxy group of the aromatic epoxy resin. Moreover, these aromatic dicarboxylic acids (B) can be used alone or in combination of two or more.
前記芳香族エポキシ樹脂（Ｃ）は、芳香環を有するエポキシ樹脂である。この芳香族エポキシ樹脂（Ｃ）としては、例えば、テトラメチルビフェノール型エポキシ樹脂等のビフェノール型エポキシ樹脂；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；ジシクロペンタジエン変性の芳香族二官能エポキシ樹脂；ジヒドロキシナフタレン類をエポキシ化してなるジヒドロキシナフタレン型エポキシ樹脂；芳香族二価カルボン酸のグリシジルエステル型樹脂；キシレノールから誘導された二官能エポキシ樹脂、ナフタレンアラルキルエポキシ樹脂；これら芳香族二官能エポキシ樹脂をジシクロペンタジエンで変性したエポキシ樹脂；これら芳香族二官能エポキシ樹脂を二塩基酸類で変性したエステル変性エポキシ樹脂等が挙げられる。これらの芳香族エポキシ樹脂（Ｃ）の中でも、前記芳香族ジカルボン酸（Ｂ）との反応でエポキシ基が開環し生じる２級水酸基の前記多官能アクリレート（Ａ）のアクリロイル基との反応性が高いことから、ビスフェノールＡ型エポキシ樹脂が好ましい。また、これらの芳香族エポキシ樹脂（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 aromatic epoxy resin (C) is an epoxy resin having an aromatic ring. Examples of the aromatic epoxy resin (C) include biphenol type epoxy resins such as tetramethylbiphenol type epoxy resins; bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; Dicyclopentadiene-modified aromatic bifunctional epoxy resin; dihydroxynaphthalene type epoxy resin obtained by epoxidizing dihydroxynaphthalene; glycidyl ester type resin of aromatic divalent carboxylic acid; bifunctional epoxy resin derived from xylenol, naphthalene aralkyl Epoxy resins; epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dicyclopentadiene; ester-modified epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dibasic acids, etc. It is. Among these aromatic epoxy resins (C), the reactivity of the secondary hydroxyl group generated by the ring opening of the epoxy group by the reaction with the aromatic dicarboxylic acid (B) with the acryloyl group of the polyfunctional acrylate (A) is high. Since it is high, bisphenol A type epoxy resin is preferable. Moreover, these aromatic epoxy resins (C) can be used alone or in combination of two or more.
前記カルボン酸（Ｄ）は、重合性不飽和基を有するカルボン酸である。このカルボン酸（Ｄ）としては、例えば、アクリル酸、メタクリル酸等が挙げられる。これらのカルボン酸（Ｄ）の中でも、活性エネルギー線照射による硬化性が良好なことから、アクリル酸が好ましい。また、これらのカルボン酸（Ｄ）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 carboxylic acid (D) is a carboxylic acid having a polymerizable unsaturated group. Examples of the carboxylic acid (D) include acrylic acid and methacrylic acid. Among these carboxylic acids (D), acrylic acid is preferable because of its good curability by active energy ray irradiation. These carboxylic acids (D) can be used alone or in combination of two or more.
本発明の活性エネルギー線硬化性組成物は、下記の２つの工程により製造することができる。
［第１工程］
多官能アクリレート（Ａ）と、芳香族ジカルボン酸（Ｂ）と、芳香族エポキシ樹脂（Ｃ）とを反応させる工程。
［第２工程］
第１工程で得られた反応物に、重合性不飽和基を有するカルボン酸（Ｄ）を反応させる工程。The active energy ray-curable composition of the present invention can be produced by the following two steps.
[First step]
The process with which a polyfunctional acrylate (A), aromatic dicarboxylic acid (B), and an aromatic epoxy resin (C) are made to react.
[Second step]
The process with which the carboxylic acid (D) which has a polymerizable unsaturated group is made to react with the reaction material obtained at the 1st process.
上記の第１工程では、芳香族ジカルボン酸（Ｂ）のカルボキシル基と、芳香族エポキシ樹脂（Ｃ）のエポキシ基とが、エポキシ基の開環付加反応により結合し、これにより生じた２級水酸基が、多官能アクリレート（Ａ）のアクリロイル基とマイケル付加反応により反応する。したがって、得られる反応物は、前記芳香族ジカルボン酸（Ｂ）と、前記芳香族エポキシ樹脂（Ｃ）とが反応して生じたポリマー鎖が、前記多官能アクリレート（Ａ）によって架橋された構造を有するものと考えられる。また、例えば、多官能アクリレート（Ａ）にエチレンオキサイド変性ペンタエリスリトールトリアクリレートを用い、芳香族ジカルボン酸（Ｂ）にイソフタル酸を用い、芳香族エポキシ樹脂（Ｃ）にビスフェノールＡ型エポキシ樹脂を用いた場合の反応の進行は、下記の（反応式１）のようになるものと考えられる。なお、マイケル付加反応後の前記芳香族ジカルボン酸（Ｂ）と前記芳香族エポキシ樹脂（Ｃ）とが反応したセグメントについては略記している。 In said 1st process, the carboxyl group of aromatic dicarboxylic acid (B) and the epoxy group of aromatic epoxy resin (C) couple | bond together by the ring-opening addition reaction of an epoxy group, and the secondary hydroxyl group produced | generated by this Reacts with the acryloyl group of the polyfunctional acrylate (A) by a Michael addition reaction. Therefore, the obtained reaction product has a structure in which the polymer chain formed by the reaction of the aromatic dicarboxylic acid (B) and the aromatic epoxy resin (C) is cross-linked by the polyfunctional acrylate (A). It is thought to have. Further, for example, ethylene oxide-modified pentaerythritol triacrylate is used for the polyfunctional acrylate (A), isophthalic acid is used for the aromatic dicarboxylic acid (B), and bisphenol A type epoxy resin is used for the aromatic epoxy resin (C). The progress of the reaction in this case is considered to be as shown in the following (Reaction Formula 1). In addition, the segment which the said aromatic dicarboxylic acid (B) after the Michael addition reaction reacted with the said aromatic epoxy resin (C) is abbreviated.
上記の第１工程での前記芳香族エポキシ樹脂（Ｃ）の使用量は、前記芳香族ジカルボン酸（Ｂ）が有するカルボキシル基１モルに対して、１．１〜３となる範囲であり、１．５〜３となる範囲が好ましい。芳香族エポキシ樹脂（Ｃ）が有するエポキシ基を過剰にして用いることで、第１工程で得られる反応物は、エポキシ基を有するものとなる。 The usage-amount of the said aromatic epoxy resin (C) in said 1st process is 1 .. with respect to 1 mol of carboxyl groups which the said aromatic dicarboxylic acid (B) has. A range of 1 to 3, range virtuous preferable to be 1.5 to 3. By using the epoxy group of the aromatic epoxy resin (C) in excess, the reaction product obtained in the first step has an epoxy group.
また、上記の第１工程での前記多官能アクリレート（Ａ）の使用量は、前記芳香族ジカルボン酸（Ｂ）及び前記芳香族エポキシ樹脂（Ｃ）の合計量１００質量部に対して、２０〜３００質量部の範囲が好ましく、５０〜２００質量部の範囲がより好ましく、８０〜１２０質量部の範囲がさらに好ましい。 Moreover, the usage-amount of the said polyfunctional acrylate (A) in said 1st process is 20-20 with respect to 100 mass parts of total amounts of the said aromatic dicarboxylic acid (B) and the said aromatic epoxy resin (C). The range of 300 parts by mass is preferable, the range of 50 to 200 parts by mass is more preferable, and the range of 80 to 120 parts by mass is more preferable.
また、上記の第１工程は、触媒（Ｅ）として、反応を制御しやすいことから、トリフェニルホスフィンの存在下で行うことが重要である。
Moreover, it is important to perform said 1st process in presence of a triphenylphosphine from a catalyst (E) being easy to control reaction .
さらに、上記の第１工程においては、重合禁止剤（Ｆ）の存在下で行うことが好ましく、この重合禁止剤（Ｆ）としては、ニトロソフェニルヒドロキシルアミンアンモニウム塩等のニトロソ系重合禁止剤；ハイドロキノン、メトキノン（ハイドロキノンモノメチルエーテル）、ベンゾキノン等のキノン系重合禁止剤；Ｎ，Ｎ−ジフェニルピクリルヒドラジル（ＤＰＰＨ）、トリフェニルメチル、ブチルヒドロキシトルエン等のラジカル捕獲剤；ベンゾトリアゾール系の酸化防止剤などが挙げられる。これらの重合禁止剤（Ｆ）の中でも、樹脂への溶解性を高いことから、メトキノンが好ましい。また、これらの重合禁止剤（Ｆ）は、単独で用いることも２種以上併用することもできる。 Furthermore, the first step is preferably carried out in the presence of a polymerization inhibitor (F). As the polymerization inhibitor (F), a nitroso polymerization inhibitor such as nitrosophenylhydroxylamine ammonium salt; hydroquinone , Quinone polymerization inhibitors such as methoquinone (hydroquinone monomethyl ether) and benzoquinone; radical scavengers such as N, N-diphenylpicrylhydrazyl (DPPH), triphenylmethyl and butylhydroxytoluene; benzotriazole antioxidants Etc. Among these polymerization inhibitors (F), methoquinone is preferred because of its high solubility in the resin. These polymerization inhibitors (F) can be used alone or in combination of two or more.
また、上記の第１工程での反応温度は、エポキシ開環反応及び付加反応が良好に進行することから、１００〜１４０℃の範囲が好ましく、１１０〜１３０℃の範囲がより好ましい。 In addition, the reaction temperature in the first step is preferably in the range of 100 to 140 ° C., more preferably in the range of 110 to 130 ° C., since the epoxy ring-opening reaction and the addition reaction proceed well.
上記の第１工程により得られる反応物のエポキシ当量は、１００〜２，０００ｇ／ｅｑ．の範囲が好ましく、１００〜５００ｇ／ｅｑ．の範囲がより好ましく、１００〜３００ｇ／ｅｑ．の範囲がさらに好ましい。また、酸価については、０．１〜３．０の範囲が好ましく、０．１〜２．０の範囲がより好ましく、０．１〜１．０の範囲がさらに好ましい。 The epoxy equivalent of the reaction product obtained by the first step is 100 to 2,000 g / eq. The range of 100 to 500 g / eq. Is more preferable, 100-300 g / eq. The range of is more preferable. Moreover, about the acid value, the range of 0.1-3.0 is preferable, the range of 0.1-2.0 is more preferable, and the range of 0.1-1.0 is further more preferable.
一方、上記の第２工程では、第１工程で得られた反応物が有するエポキシ基に、アクリル酸等の重合性不飽和基を有するカルボン酸（Ｄ）のカルボキシル基を反応させることにより、第１工程で得られた反応物に重合性不飽和基を導入することができる。この反応については、例えば、第１工程で得られた反応物が上記の（反応式１）で示したものであり、カルボン酸（Ｄ）にアクリル酸を用いた場合、下記の（反応式２）のようになる。 On the other hand, in the second step, the epoxy group of the reaction product obtained in the first step is reacted with the carboxyl group of the carboxylic acid (D) having a polymerizable unsaturated group such as acrylic acid, thereby causing the first step. A polymerizable unsaturated group can be introduced into the reaction product obtained in one step. Regarding this reaction, for example, when the reaction product obtained in the first step is the one shown in (Reaction Formula 1) and acrylic acid is used as the carboxylic acid (D), the following (Reaction Formula 2) )become that way.
また、この第１工程で得られた反応物と重合性不飽和基を有するカルボン酸（Ｄ）との反応についても、必要に応じて、第１工程で説明した前記触媒（Ｅ）及び重合禁止剤（Ｆ）を用いることができる。 In addition, for the reaction between the reaction product obtained in the first step and the carboxylic acid (D) having a polymerizable unsaturated group, the catalyst (E) described in the first step and the polymerization prohibition are also necessary. Agent (F) can be used.
上記の第１工程及び第２工程を経て得られる本発明の活性エネルギー線硬化性組成物のエポキシ当量は、組成物の安定性が良好となることから、５，０００〜５０，０００ｇ／ｅｑ．の範囲が好ましく、１０，０００〜５０，０００ｇ／ｅｑ．の範囲がより好ましく、１４，０００〜５０，０００ｇ／ｅｑ．の範囲がさらに好ましい。また、酸価については、組成物の安定性の観点から０．５〜１０の範囲が好ましく、０．５〜５の範囲がより好ましく、０．５〜３の範囲がさらに好ましい。 The epoxy equivalent of the active energy ray-curable composition of the present invention obtained through the first step and the second step is 5,000 to 50,000 g / eq. Is preferable, and 10,000 to 50,000 g / eq. Is more preferable, and 14,000 to 50,000 g / eq. The range of is more preferable. Moreover, about the acid value, the range of 0.5-10 is preferable from a stability viewpoint of a composition, The range of 0.5-5 is more preferable, The range of 0.5-3 is further more preferable.
また、本発明の活性エネルギー線硬化性組成物には、さらに多官能アクリレート（Ａ’）を加えてもよい。この多官能アクリレート（Ａ’）を加える場合は、上記の第２工程時に加えても、第２工程後に加えても構わない。多官能アクリレート（Ａ’）としては、多官能アクリレート（Ａ）と同様のものを用いることができ、多官能アクリレート（Ａ）と同一のものであっても、異なるものであっても構わないが、エチレンオキサイド変性トリメチロールプロパントリアクリレートが好ましい。また、これらの多官能アクリレート（Ａ’）は、単独で用いることも２種以上併用することもできる。 Further, a polyfunctional acrylate (A ′) may be further added to the active energy ray-curable composition of the present invention. When this polyfunctional acrylate (A ′) is added, it may be added during the second step or after the second step. The polyfunctional acrylate (A ′) can be the same as the polyfunctional acrylate (A), and may be the same as or different from the polyfunctional acrylate (A). Ethylene oxide-modified trimethylolpropane triacrylate is preferred. These polyfunctional acrylates (A ′) can be used alone or in combination of two or more.
本発明の活性エネルギー線硬化性塗料は、本発明の活性エネルギー線硬化性組成物を含有するものであるが、その他の配合物として、顔料、染料、体質顔料、有機又は無機フィラー、活性エネルギー線硬化性単量体、活性エネルギー線硬化性オリゴマー、有機溶剤、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 active energy ray-curable coating material of the present invention contains the active energy ray-curable composition of the present invention, and other compounds include pigments, dyes, extender pigments, organic or inorganic fillers, active energy rays. Curing monomer, active energy ray curable oligomer, organic solvent, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weather stabilizer, heat stabilizer, ultraviolet absorber, antioxidant, leveling agent Additives such as pigment dispersants can be used.
本発明の活性エネルギー線硬化性塗料は、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（Ｇ）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（Ｇ）や光増感剤を添加する必要はない。 The active energy ray-curable 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. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator (G) 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 G) or a photosensitizer.
前記光重合開始剤（Ｇ）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 (G) 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；ミヒラーケトン、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（Ｇ）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 (G) 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 initiators and photosensitizers 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 coating material of the present invention. 10 mass% is more preferable.
また、本発明の活性エネルギー線硬化性塗料は、各種物品を塗装する塗料として用いることができる。本発明の活性エネルギー線硬化性塗料を塗装することのできる物品としては、テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；パソコン、スマートフォン、携帯電話、デジタルカメラ、ゲーム機等の電子機器の筐体；自動車、鉄道車輌等の各種車輌の内装材；化粧板等の各種建材；家具等の木工材料、人工・合成皮革；ＦＲＰ浴槽などが挙げられる。 Moreover, the active energy ray-curable coating material of the present invention can be used as a coating material for coating various articles. Articles that can be coated with the active energy ray-curable paint of the present invention include housings for home appliances such as TVs, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Equipment casings; interior materials for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; woodwork materials such as furniture; artificial and synthetic leather; FRP bathtubs.
また、本発明の活性エネルギー線硬化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。 In addition, the application method of the active energy ray-curable paint of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, Examples of the method include spin coater, dipping, screen printing, spraying, applicator, and bar coater.
本発明の活性エネルギー線硬化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 ray for curing the active energy ray-curable coating of the present invention is ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. Curing devices include, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, and ultraviolet rays that use natural light as a light source. Or an electron beam by a scanning type or curtain type electron beam accelerator.
本発明の活性エネルギー線硬化性印刷インキは、本発明の活性エネルギー線硬化性組成物を含有するものであるが、その他、各種印刷方式に適した配合物が配合されたものである。例えば、平版印刷用印刷インキの場合は、顔料、染料、体質顔料、パラフィンワックス、ポリオレフィンワックス、有機溶剤、顔料分散剤等の添加剤を使用することができる。 The active energy ray curable printing ink of the present invention contains the active energy ray curable composition of the present invention, and is formulated with other blends suitable for various printing methods. For example, in the case of printing ink for lithographic printing, additives such as pigments, dyes, extender pigments, paraffin wax, polyolefin wax, organic solvents, and pigment dispersants can be used.
また、本発明の活性エネルギー線硬化性印刷インキの場合も、必要に応じて、光重合開始剤や光増感剤を配合し、その配合量も塗料の場合と同様である。さらに、効果の際に用いる活性エネルギー線及びそれを照射する装置も同様なものを用いることができる。 Moreover, also in the case of the active energy ray-curable printing ink of the present invention, a photopolymerization initiator and a photosensitizer are blended as necessary, and the blending amount is the same as in the case of the paint. Furthermore, the same thing can be used also about the active energy ray used in the case of an effect, and the apparatus which irradiates it.
また、本発明の活性エネルギー線硬化性印刷インキは、各種被印刷物を印刷するものとして用いることができる。当該被印刷物としては、カタログ、パンフレット、化粧品パッケージ等に用いる紙基材；ポリプロピレンフィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム等の各種食品包装用資材に用いられるフィルムなどが挙げられる。 Moreover, the active energy ray-curable printing ink of the present invention can be used for printing various printed materials. Examples of the printed material include paper base materials used for catalogs, pamphlets, cosmetic packages, and the like; films used for various food packaging materials such as polypropylene films and polyethylene terephthalate (PET) films.
また、本発明の活性エネルギー線硬化性印刷インキの印刷方法としては、例えば、平版印刷、グラビア印刷、グラビアオフセット印刷、フレキソ印刷等が挙げられる。 Examples of the printing method of the active energy ray-curable printing ink of the present invention include lithographic printing, gravure printing, gravure offset printing, flexographic printing, and the like.
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、得られたものの酸価は、ＪＩＳ試験方法Ｋ ００７０−１９９２に準拠して測定し、エポキシ当量は、ＪＩＳ試験方法Ｋ ７２３６：２００１に準拠して測定した。 Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the acid value of what was obtained was measured based on JIS test method K 0070-1992, and the epoxy equivalent was measured based on JIS test method K 7236: 2001.
（実施例１）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、エチレンオキサイド変性トリメチロールプロパントリアクリレート（以下、「ＥＯＴＭＰＴＡ」と略記する。）１７７．５質量部、ビスフェノールＡ型エポキシ樹脂（ダウ・ケミカル日本株式会社製「ＤＥＲ３３１」、エポキシ当量１８５ｇ／ｅｑ．；以下、「Ｂｉｓ−Ａ型エポキシ樹脂」と略記する。）１４５質量部、テレフタル酸（以下、「ＴＰＡ」と略記する。）３２質量部、ジブチルヒドロキシトルエン（重合禁止剤；以下、「ＢＨＴ」と略記する。）１．８質量部、及びメトキノン（重合禁止剤；以下、「ＭＱ」と略記する。）０．２質量部を仕込み、１２０℃に昇温した後、トリフェニルホスフィン（触媒；以下、「ＴＰＰ」と略記する。）２．７質量部を加えた。１２０℃で５時間反応を継続し、反応溶液のエポキシ当量が１，０５０ｇ／ｅｑ．となった時点で、アクリル酸２４質量部、ＥＯＴＭＰＴＡ１０５質量部、及びＴＰＰ１．２質量部を仕込んだ後、さらに１２０℃で２時間反応を行うことで、エポキシ当量が１５，０００ｇ／ｅｑ．であり、酸価が３．４である活性エネルギー線硬化性組成物（１）を得た。Example 1
In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (hereinafter abbreviated as “EOTMPTA”), bisphenol A type epoxy resin (Dow “DER331” manufactured by Chemical Japan Co., Ltd., epoxy equivalent of 185 g / eq., Hereinafter abbreviated as “Bis-A type epoxy resin”) 145 parts by mass, terephthalic acid (hereinafter abbreviated as “TPA”) 32 masses Parts, dibutylhydroxytoluene (polymerization inhibitor; hereinafter abbreviated as “BHT”) 1.8 parts by mass, and methoquinone (polymerization inhibitor; hereinafter abbreviated as “MQ”) 0.2 parts by mass. The temperature was raised to 120 ° C., and 2.7 parts by mass of triphenylphosphine (catalyst; hereinafter abbreviated as “TPP”) was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 24 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further carried out at 120 ° C. for 2 hours, so that the epoxy equivalent was 15,000 g / eq. And an active energy ray-curable composition (1) having an acid value of 3.4 was obtained.
（実施例２）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、ＥＯＴＭＰＴＡ１７７．５質量部、Ｂｉｓ−Ａ型エポキシ樹脂１４５質量部、イソフタル酸（以下、「ＩＰＡ」と略記する。）３２質量部、ＢＨＴ１．８質量部、及びＭＱ０．２質量部を仕込み、１２０℃に昇温した後、ＴＰＰ２．７質量部を加えた。１２０℃で５時間反応を継続し、反応溶液のエポキシ当量が１，０５０ｇ／ｅｑ．となった時点で、アクリル酸２５質量部、ＥＯＴＭＰＴＡ１０５質量部、及びＴＰＰ１．２質量部を仕込んだ後、さらに１２０℃で２時間反応を行うことで、エポキシ当量が１６，０００ｇ／ｅｑ．であり、酸価が２．１である活性エネルギー線硬化性組成物（２）を得た。(Example 2)
In a four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 177.5 parts by mass of EOTMPTA, 145 parts by mass of Bis-A type epoxy resin, 32 parts by mass of isophthalic acid (hereinafter abbreviated as “IPA”), After charging 1.8 parts by mass of BHT and 0.2 parts by mass of MQ and raising the temperature to 120 ° C., 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 25 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further performed at 120 ° C. for 2 hours, so that the epoxy equivalent was 16,000 g / eq. And an active energy ray-curable composition (2) having an acid value of 2.1 was obtained.
（実施例３）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、ＥＯＴＭＰＴＡ１７７．５質量部、Ｂｉｓ−Ａ型エポキシ樹脂１４９．５質量部、ＩＰＡ２１質量部、ＢＨＴ１．８質量部、及びＭＱ０．２質量部を仕込み、１２０℃に昇温した後、ＴＰＰ２．７質量部を加えた。１２０℃で５時間反応を継続し、反応溶液のエポキシ当量が１，０５０ｇ／ｅｑ．となった時点で、アクリル酸２８質量部、ＥＯＴＭＰＴＡ１０５質量部、及びＴＰＰ１．２質量部を仕込んだ後、さらに１２０℃で２時間反応を行うことで、エポキシ当量が１５，５００ｇ／ｅｑ．であり、酸価が１．５である活性エネルギー線硬化性組成物（３）を得た。(Example 3)
In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, EOTMPTA 177.5 parts by mass, Bis-A type epoxy resin 149.5 parts by mass, IPA 21 parts by mass, BHT 1.8 parts by mass, and MQ 0.2 parts by mass Parts were charged and the temperature was raised to 120 ° C., and then 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 28 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further carried out at 120 ° C. for 2 hours, so that the epoxy equivalent was 15,500 g / eq. And an active energy ray-curable composition (3) having an acid value of 1.5 was obtained.
（実施例４）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、トリメチロールプロパントリアクリレート（以下、「ＴＭＰＴＡ」と略記する。）１７７．５質量部、Ｂｉｓ−Ａ型エポキシ樹脂１４５質量部、ＩＰＡ３２質量部、ＢＨＴ１．８質量部、及びＭＱ０．２質量部を仕込み、１２０℃に昇温した後、ＴＰＰ２．７質量部を加えた。１２０℃で５時間反応を継続し、反応溶液のエポキシ当量が１，０５０ｇ／ｅｑ．となった時点で、アクリル酸２５質量部、ＥＯＴＭＰＴＡ１０５質量部、及びＴＰＰ１．２質量部を仕込んだ後、さらに１２０℃で２時間反応を行うことで、エポキシ当量が１５，１００ｇ／ｅｑ．であり、酸価が２．５である活性エネルギー線硬化性組成物（４）を得た。(Example 4)
In a four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 177.5 parts by mass of trimethylolpropane triacrylate (hereinafter abbreviated as “TMPTA”), 145 parts by mass of Bis-A type epoxy resin, IPA32 After adding a mass part, 1.8 mass parts of BHT, and 0.2 mass part of MQ, and heating up at 120 degreeC, 2.7 mass parts of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 25 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further performed at 120 ° C. for 2 hours, so that the epoxy equivalent was 15,100 g / eq. And an active energy ray-curable composition (4) having an acid value of 2.5 was obtained.
（実施例５）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、グリセリンプロポキシトリアクリレート（以下、「ＧＰＴＡ」と略記する。）１７７．５質量部、Ｂｉｓ−Ａ型エポキシ樹脂１４５質量部、ＩＰＡ３２質量部、ＢＨＴ１．８質量部、及びＭＱ０．２質量部を仕込み、１２０℃に昇温した後、ＴＰＰ２．７質量部を加えた。１２０℃で５時間反応を継続し、反応溶液のエポキシ当量が１，０５０ｇ／ｅｑ．となった時点で、アクリル酸２４質量部、ＥＯＴＭＰＴＡ１０５質量部、及びＴＰＰ１．２質量部を仕込んだ後、さらに１２０℃で２時間反応を行うことで、エポキシ当量が１６，０００ｇ／ｅｑ．であり、酸価が２．２である活性エネルギー線硬化性組成物（５）を得た。(Example 5)
In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, 177.5 parts by mass of glycerin propoxytriacrylate (hereinafter abbreviated as “GPTA”), 145 parts by mass of Bis-A type epoxy resin, 32 parts by mass of IPA Part, BHT 1.8 parts by mass, and MQ 0.2 parts by mass were heated to 120 ° C., and then 2.7 parts by mass of TPP was added. The reaction was continued at 120 ° C. for 5 hours, and the epoxy equivalent of the reaction solution was 1,050 g / eq. Then, after charging 24 parts by mass of acrylic acid, 105 parts by mass of EOTMPTA, and 1.2 parts by mass of TPP, the reaction was further carried out at 120 ° C. for 2 hours, so that the epoxy equivalent was 16,000 g / eq. And an active energy ray-curable composition (5) having an acid value of 2.2 was obtained.
上記の実施例１〜５で得られた活性エネルギー線硬化性組成物（１）〜（５）の原料組成、エポキシ当量、及び酸価を表１にまとめた。 Table 1 summarizes the raw material compositions, epoxy equivalents, and acid values of the active energy ray-curable compositions (1) to (5) obtained in Examples 1 to 5 above.
（比較例１）
攪拌機、温度計及び冷却管を備えた４つ口のフラスコに、Ｂｉｓ−Ａ型エポキシ樹脂１４５質量部、アクリル酸５６質量部、ＢＨＴ１．８質量部、及びＭＱ０．２質量部を仕込み、１２０℃に昇温した後、ＴＰＰ１．２質量部を加えた。次いで、１２０℃で５時間反応を行うことで、エポキシ当量が１５，０００ｇ／ｅｑ．であり、酸価が１．０である活性エネルギー線硬化性組成物（Ｒ１）を得た。(Comparative Example 1)
A four-necked flask equipped with a stirrer, a thermometer and a cooling tube was charged with 145 parts by mass of a Bis-A type epoxy resin, 56 parts by mass of acrylic acid, 1.8 parts by mass of BHT, and 0.2 parts by mass of MQ, and 120 ° C. Then, 1.2 parts by mass of TPP was added. Subsequently, by reacting at 120 ° C. for 5 hours, an epoxy equivalent of 15,000 g / eq. And an active energy ray-curable composition (R1) having an acid value of 1.0 was obtained.
（実施例６）
［活性エネルギー線硬化性塗料の調製］
上記の実施例１で得られた活性エネルギー線硬化性組成物（１）１００質量部、光重合開始剤（ＢＡＳＦジャパン株式会社製「イルガキュア１８４」；１−ヒドロキシシクロヘキシル−フェニルケトン）４質量部、及び酢酸ブチル２０質量部を混合して、活性エネルギー線硬化性塗料（１）を得た。次いで、得られた活性エネルギー線硬化性塗料（１）の硬化塗膜について、下記の耐擦傷性の評価を行った。(Example 6)
[Preparation of active energy ray curable paint]
100 parts by mass of the active energy ray-curable composition (1) obtained in Example 1 above, 4 parts by mass of a photopolymerization initiator (“Irgacure 184”; 1-hydroxycyclohexyl-phenyl ketone) manufactured by BASF Japan Ltd., And 20 mass parts of butyl acetate was mixed and the active energy ray-curable coating material (1) was obtained. Subsequently, the following scratch resistance evaluation was performed about the cured coating film of the obtained active energy ray-curable coating material (1).
［耐擦傷性の評価］
上記で得られた活性エネルギー線硬化性塗料（１）を、アプリケーターを用いてガラス板（厚さ２ｍｍ）上に乾燥膜厚１０μｍとなるように塗布し、溶剤を乾燥後、８０Ｗ／ｃｍの高圧水銀ランプを用いて０．８Ｊ／ｃｍ２の紫外線照射量で硬化させて、耐擦傷性の評価用塗膜を得た。次いで、直径２７ｍｍの円形の治具にスチールウール（日本スチールウール株式会社製「ボンスター Ｎｏ，００００」）を取り付けた磨耗試験機（５００ｇ／ｃｍ２荷重）にて、得られた評価用塗膜の表面を１００往復磨耗させた。試験後の塗膜をヘイズメーター（日本電色工業株式会社製「ＮＤＨ５０００」）で測定し、得られたヘイズ値から、下記の基準にしたがって耐擦傷性を評価した。
○：ヘイズ値が５未満である。
△：ヘイズ値が５以上１０未満である。
×：ヘイズ値が１０以上である。[Evaluation of scratch resistance]
The active energy ray-curable paint (1) obtained above was applied on a glass plate (thickness 2 mm) using an applicator so as to have a dry film thickness of 10 μm, and after drying the solvent, a high pressure of 80 W / cm. Curing was performed using a mercury lamp at an ultraviolet irradiation amount of 0.8 J / cm 2 to obtain a coating film for evaluation of scratch resistance. Next, the obtained coating film for evaluation was obtained with a wear tester (500 g / cm 2 load) in which steel wool (“Bonster No. 0000” manufactured by Nippon Steel Wool Co., Ltd.) was attached to a circular jig having a diameter of 27 mm. The surface was worn 100 reciprocating times. The coating film after the test was measured with a haze meter (“NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the scratch resistance was evaluated according to the following criteria from the obtained haze value.
○: Haze value is less than 5.
Δ: Haze value is 5 or more and less than 10.
X: Haze value is 10 or more.
（実施例７〜１０及び比較例２）
実施例６で用いた活性エネルギー線硬化性組成物（１）に代えて、実施例２〜５及び比較例１で得られた活性エネルギー線硬化性組成物（２）〜（５）及び（Ｒ１）を用いた以外は同様に操作して、活性エネルギー線硬化性塗料（２）〜（５）及び（Ｒ１）を調製し、硬化塗膜を得て、耐擦傷性の評価を行った。(Examples 7 to 10 and Comparative Example 2)
Instead of the active energy ray-curable composition (1) used in Example 6, the active energy ray-curable compositions (2) to (5) and (R1) obtained in Examples 2 to 5 and Comparative Example 1 were used. The active energy ray-curable paints (2) to (5) and (R1) were prepared in the same manner except that was used, and a cured coating film was obtained to evaluate the scratch resistance.
上記の実施例６〜１０及び比較例２で得られた活性エネルギー線硬化性塗料の組成と、耐擦傷性の評価結果を表２にまとめた。 Table 2 summarizes the compositions of the active energy ray-curable coatings obtained in Examples 6 to 10 and Comparative Example 2 and the evaluation results of scratch resistance.
本発明の活性エネルギー線硬化性組成物を用いた実施例６〜１０の活性エネルギー線硬化性塗料の硬化塗膜は、スチールウールによる摩耗後のヘイズ値が１〜２％と非常に小さく、高い耐擦傷性を有することが分かった。 The cured coating films of the active energy ray-curable coatings of Examples 6 to 10 using the active energy ray-curable composition of the present invention have a very small and high haze value of 1 to 2% after abrasion with steel wool. It was found to have scratch resistance.
一方、比較例２の活性エネルギー線硬化性塗料は、本発明で用いる多官能アクリレート（Ａ）及び芳香族ジカルボン酸（Ｂ）を用いなかった活性エネルギー線硬化性組成物を用いた例であるが、スチールウールによる摩耗後のヘイズ値が１１％と高く、耐擦傷性に劣っていることが分かった。 On the other hand, the active energy ray-curable coating material of Comparative Example 2 is an example using an active energy ray-curable composition that does not use the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention. It was found that the haze value after abrasion with steel wool was as high as 11% and the scratch resistance was poor.
（実施例１１）
［活性エネルギー線硬化性印刷インキの調製］
上記の実施例１で得られた活性エネルギー線硬化性組成物（１）２３質量部、赤色顔料（Ｐｉｇｍｅｎｔ Ｒｅｄ ５７−１）１９質量部、黄色顔料（Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １３）３質量部、直鎖状ポリエステルアクリレート（ＵＳＢケミカルズ社製「エベクリル６５７」；以下、「ＰＥｓＡ」と略記する。）２５質量部、ＴＭＰＴＡ１３質量部、タルク８質量部、ポリエチレンワックス５質量部、光重合開始剤（ＢＡＳＦジャパン株式会社製「イルガキュア９０７」、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；以下、「光重合開始剤（１）」と略記する。）２質量部、光重合開始剤（４，４’−ジエチルアミノベンゾフェノン；以下、「光重合開始剤（２）」と略記する。）２質量部及びを混合した後、３本ロールで練肉して、活性エネルギー線硬化性印刷インキ（１）を得た。次いで、得られた活性エネルギー線硬化性印刷インキ（１）について、下記の耐ミスチング性を評価し、また、活性エネルギー線硬化性印刷インキ（１）の硬化塗膜について、下記の密着性及び耐溶剤性の評価を行った。(Example 11)
[Preparation of active energy ray-curable printing ink]
23 parts by mass of the active energy ray-curable composition (1) obtained in Example 1 above, 19 parts by mass of a red pigment (Pigment Red 57-1), 3 parts by mass of a yellow pigment (Pigment Yellow 13), linear 25 parts by mass of polyester acrylate (“Evekril 657” manufactured by USB Chemicals; hereinafter abbreviated as “PEsA”), 13 parts by mass of TMPTA, 8 parts by mass of talc, 5 parts by mass of polyethylene wax, photopolymerization initiator (BASF Japan Ltd.) “Irgacure 907”, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one; hereinafter abbreviated as “photopolymerization initiator (1)”) 2 parts by mass, photopolymerization initiator (4,4′-diethylaminobenzophenone; hereinafter abbreviated as “photopolymerization initiator (2)”) 2 parts by mass and After, the mixture was kneaded with a three-roll to obtain an active energy ray-curable printing ink (1). Subsequently, about the obtained active energy ray-curable printing ink (1), the following misting resistance was evaluated, and about the cured coating film of the active energy ray-curable printing ink (1), the following adhesion and resistance. Solvent properties were evaluated.
［耐ミスチング性の評価］
上記で得られた活性エネルギー線硬化性印刷インキ（１）を、インコメーター（Ｔｈｗｉｎｇ−Ａｌｂｅｒｔ社「Ｍｏｄｅｌ １０１」）を用いて、１２００ｒｐｍ、３２℃の条件で１分間インキのランニングを行い、ミスチングの状態（発生するミスト量）を目視で観察して、下記の基準にしたがって耐ミスチング性を評価した。
５：ミストが発生しない。
４：ごくわずかにミストが発生する。
３：ややミストが発生する。
２：ミストが発生する。
１：激しくミストが発生する。[Evaluation of misting resistance]
The active energy ray-curable printing ink (1) obtained above was run for 1 minute under the conditions of 1200 rpm and 32 ° C. using an incometer (Thwing-Albert “Model 101”), and misting The state (amount of mist generated) was visually observed, and the misting resistance was evaluated according to the following criteria.
5: No mist is generated.
4: Very little mist is generated.
3: Slight mist is generated.
2: Mist is generated.
1: Vigorous mist is generated.
［密着性の評価］
上記で得られた活性エネルギー線硬化性印刷インキ（１）を、基材であるポリエチレンテレフタレートフィルム（東洋紡績株式会社製のコロナ処理ＰＥＴフィルム；厚さ５０μｍ）にバーコーター＃４を用いて塗布し、８０Ｗ／ｃｍの高圧水銀ランプを用いて０．８Ｊ／ｃｍ２の紫外線照射量で硬化させて、密着性の評価用塗膜を得た。得られた評価用塗膜の表面にセロハンテープを貼り、勢いよく剥がした際の塗膜の基材からの剥離状態を目視で観察して、下記の基準にしたがって密着性を評価した。
◎：基材から塗膜が全く剥離しない。
○：基材からは剥離しないが、塗膜中で凝集破壊を生じて塗膜の一部が剥離する。
△：基材から塗膜の一部が剥離する。
×：基材からセロハンテープを貼った部分が全面剥離する。[Evaluation of adhesion]
The active energy ray-curable printing ink (1) obtained above was applied to a polyethylene terephthalate film (corona-treated PET film manufactured by Toyobo Co., Ltd .; thickness 50 μm) as a base material using a bar coater # 4. The film was cured with an ultraviolet irradiation amount of 0.8 J / cm 2 using an 80 W / cm high-pressure mercury lamp to obtain a coating film for evaluating adhesion. A cellophane tape was applied to the surface of the obtained coating film for evaluation, and the peeled state of the coating film from the substrate when peeled vigorously was visually observed, and the adhesion was evaluated according to the following criteria.
(Double-circle): A coating film does not peel from a base material at all.
◯: Although not peeled off from the substrate, cohesive failure occurs in the coating film, and a part of the coating film peels off.
(Triangle | delta): A part of coating film peels from a base material.
X: The part which stuck the cellophane tape from the base material peels entirely.
［耐溶剤性の評価］
上記で得られた活性エネルギー線硬化性印刷インキ（１）を、バーコーター＃４を用いて塗布し、８０Ｗ／ｃｍの高圧水銀ランプを用いて０．８Ｊ／ｃｍ２の紫外線照射量で硬化させて、耐溶剤性の評価用塗膜を得た。得られた評価用塗膜の表面にエタノールを含ませたフェルトで、１０回擦った後の塗膜表面の状態を目視で観察して、下記の基準にしたがって耐溶剤性を評価した。
○：変化なし。
△：擦れ痕が残る。
×：インキが消失し、基材が確認できる。[Evaluation of solvent resistance]
The active energy ray-curable printing ink (1) obtained above is applied using a bar coater # 4, and cured with an ultraviolet irradiation amount of 0.8 J / cm 2 using an 80 W / cm high-pressure mercury lamp. Thus, a coating film for evaluation of solvent resistance was obtained. The condition of the coating film surface after rubbing 10 times with a felt containing ethanol on the surface of the obtained coating film for evaluation was visually observed, and the solvent resistance was evaluated according to the following criteria.
○: No change.
Δ: Rub marks remain.
X: The ink disappears and the substrate can be confirmed.
（実施例１２〜１５及び比較例３）
実施例１１で用いた活性エネルギー線硬化性組成物（１）に代えて、実施例２〜５及び比較例１で得られた活性エネルギー線硬化性組成物（２）〜（５）及び（Ｒ１）を用いた以外は同様に操作して、活性エネルギー線硬化性印刷インキ（２）〜（５）及び（Ｒ１）を調製した。得られた活性エネルギー線硬化性印刷インキを用いて、実施例１１と同様に、耐ミスチング性、密着性及び耐溶剤性の評価を行った。(Examples 12 to 15 and Comparative Example 3)
Instead of the active energy ray-curable composition (1) used in Example 11, the active energy ray-curable compositions (2) to (5) and (R1) obtained in Examples 2 to 5 and Comparative Example 1 were used. The active energy ray-curable printing inks (2) to (5) and (R1) were prepared in the same manner except that was used. Using the obtained active energy ray-curable printing ink, evaluation of misting resistance, adhesion and solvent resistance was carried out in the same manner as in Example 11.
（比較例４）
実施例１１で用いた活性エネルギー線硬化性組成物（１）２３質量部に代えて、比較例１で得られた活性エネルギー線硬化性組成物（Ｒ１）１０質量部及びロジン変性フェノール樹脂（ＤＩＣ株式会社製「ベッカサイト Ｆ−７３０５」）１３質量部を用いた以外は同様に操作して、活性エネルギー線硬化性印刷インキ（Ｒ２）を調製した。得られた活性エネルギー線硬化性印刷インキを用いて、実施例１１と同様に、密着性、耐ミスチング性及び耐溶剤性の評価を行った。(Comparative Example 4)
Instead of 23 parts by mass of active energy ray-curable composition (1) used in Example 11, 10 parts by mass of active energy ray-curable composition (R1) obtained in Comparative Example 1 and rosin-modified phenolic resin (DIC) Active energy ray-curable printing ink (R2) was prepared in the same manner except that 13 parts by mass of “Beccasite F-7305” manufactured by Co., Ltd. was used. Using the obtained active energy ray-curable printing ink, the adhesion, misting resistance and solvent resistance were evaluated in the same manner as in Example 11.
上記の実施例１１〜１５、比較例３及び４で得られた活性エネルギー線硬化性印刷インキの組成と、耐ミスチング性、密着性及び耐溶剤性の評価結果を表３にまとめた。 Table 3 summarizes the compositions of the active energy ray-curable printing inks obtained in Examples 11 to 15 and Comparative Examples 3 and 4, and the evaluation results of misting resistance, adhesion, and solvent resistance.
本発明の活性エネルギー線硬化性組成物を用いた実施例１１〜１５の活性エネルギー線硬化性印刷インキは、耐ミスチング性に優れることが分かった。また、本発明の活性エネルギー線硬化性印刷インキの硬化塗膜は、ポリエチレンテレフタレートフィルムに対して非常に高い密着性を有し、かつ高い耐溶剤性を有することが分かった。 It was found that the active energy ray-curable printing inks of Examples 11 to 15 using the active energy ray-curable composition of the present invention were excellent in misting resistance. Moreover, it turned out that the cured coating film of the active energy ray curable printing ink of this invention has very high adhesiveness with respect to a polyethylene terephthalate film, and has high solvent resistance.
一方、比較例３の活性エネルギー線硬化性印刷インキは、本発明で用いる多官能アクリレート（Ａ）及び芳香族ジカルボン酸（Ｂ）を用いなかった活性エネルギー線硬化性組成物を用いた例であるが、この活性エネルギー線硬化性印刷インキは、ミスト量が非常に多く、耐ミスチング性に問題があることが分かった。また、この印刷インキの硬化塗膜は、ポリエチレンテレフタレートフィルムに対して密着性に乏しく、さらに耐溶剤性が十分でないことが分かった。 On the other hand, the active energy ray-curable printing ink of Comparative Example 3 is an example using an active energy ray-curable composition that did not use the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention. However, it has been found that this active energy ray-curable printing ink has a very large amount of mist and has a problem in misting resistance. Moreover, it turned out that the cured coating film of this printing ink is poor in adhesiveness with respect to a polyethylene terephthalate film, and also solvent resistance is not enough.
比較例４の活性エネルギー線硬化性印刷インキは、本発明で用いる多官能アクリレート（Ａ）及び芳香族ジカルボン酸（Ｂ）を用いなかった活性エネルギー線硬化性組成物とロジン樹脂とを併用した例であるが、この活性エネルギー線硬化性印刷インキは、比較例３のものと比較するとミスト量が抑制できるが、この印刷インキの硬化塗膜は、ポリエチレンテレフタレートフィルムに対して密着性に乏しく、さらに耐溶剤性が全くないことが分かった。 The active energy ray-curable printing ink of Comparative Example 4 is an example in which an active energy ray-curable composition not using the polyfunctional acrylate (A) and aromatic dicarboxylic acid (B) used in the present invention and a rosin resin are used in combination. However, this active energy ray-curable printing ink can suppress the amount of mist as compared with that of Comparative Example 3, but the cured coating film of this printing ink has poor adhesion to the polyethylene terephthalate film. It was found that there was no solvent resistance.
Claims (6)
前記多官能アクリレート（Ａ）が、トリメチロールプロパントリアクリレート、エチレンオキサイド変性トリメチロールプロパントリアクリレート及びグリセリンプロポキシトリアクリレートからなる群から選ばれる少なくとも１種の多官能アクリレートであり、前記芳香族エポキシ樹脂（Ｃ）の使用量が、前記芳香族ジカルボン酸（Ｂ）が有するカルボキシル基１モルに対して、前記芳香族エポキシ樹脂（Ｃ）が有するエポキシ基が１．１〜３となる範囲であることを特徴とする活性エネルギー線硬化性組成物。 In the presence of triphenylphosphine, the polyfunctional acrylate (A), the aromatic dicarboxylic acid (B), and the aromatic epoxy resin (C) are reacted, and then a polymerizable unsaturated group is added to the obtained reaction product. An active energy ray-curable composition obtained by reacting a carboxylic acid (D) having
The polyfunctional acrylate (A) is at least one polyfunctional acrylate selected from the group consisting of trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and glycerin propoxytriacrylate, and the aromatic epoxy resin ( The amount of C) used is a range in which the epoxy group of the aromatic epoxy resin (C) is 1.1 to 3 with respect to 1 mol of the carboxyl group of the aromatic dicarboxylic acid (B). An active energy ray-curable composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013546113A JP5495087B2 (en) | 2012-03-19 | 2013-03-13 | Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012062043 | 2012-03-19 | ||
| JP2012062043 | 2012-03-19 | ||
| PCT/JP2013/057057 WO2013141117A1 (en) | 2012-03-19 | 2013-03-13 | Active energy ray-curable composition, active energy ray-curable coating material using same, and active energy ray-curable printing ink using same |
| JP2013546113A JP5495087B2 (en) | 2012-03-19 | 2013-03-13 | Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5495087B2 true JP5495087B2 (en) | 2014-05-21 |
| JPWO2013141117A1 JPWO2013141117A1 (en) | 2015-08-03 |
Family
ID=49222577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013546113A Expired - Fee Related JP5495087B2 (en) | 2012-03-19 | 2013-03-13 | Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5495087B2 (en) |
| CN (1) | CN104220478B (en) |
| IN (1) | IN2014DN08494A (en) |
| TW (1) | TWI557143B (en) |
| WO (1) | WO2013141117A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6196877B2 (en) * | 2013-10-21 | 2017-09-13 | サカタインクス株式会社 | Active energy ray-curable offset printing ink composition and printing method using the composition |
| JP6362272B2 (en) * | 2015-03-13 | 2018-07-25 | 日本化薬株式会社 | Carboxyl group-containing reactive compound, curable resin composition using the same, and use thereof. |
| JP6996284B2 (en) * | 2016-12-28 | 2022-01-17 | 荒川化学工業株式会社 | Resin and its manufacturing method, active energy ray-curable resin composition, cured product, active energy ray-curable printing ink, and printed matter. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004067814A (en) * | 2002-08-05 | 2004-03-04 | Showa Highpolymer Co Ltd | Polycarboxylic acid resin, polycarboxylic acid resin composition and its cured product |
| JP2007031576A (en) * | 2005-07-27 | 2007-02-08 | Dainippon Ink & Chem Inc | Method for producing branched polyether resin composition and method for producing acid pendant-type branched polyether resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216016A (en) * | 1988-07-01 | 1990-01-19 | Showa Highpolymer Co Ltd | Manufacture of molded form |
| KR100883047B1 (en) * | 2006-07-10 | 2009-02-11 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/thermosetting resin composition, cured product thereof and printed wiring board |
| JP5467556B2 (en) * | 2009-04-01 | 2014-04-09 | 東京インキ株式会社 | Lithographic printing ink and printed matter printed using the same |
-
2013
- 2013-03-13 WO PCT/JP2013/057057 patent/WO2013141117A1/en active Application Filing
- 2013-03-13 CN CN201380015498.2A patent/CN104220478B/en not_active Expired - Fee Related
- 2013-03-13 JP JP2013546113A patent/JP5495087B2/en not_active Expired - Fee Related
- 2013-03-13 IN IN8494DEN2014 patent/IN2014DN08494A/en unknown
- 2013-03-18 TW TW102109556A patent/TWI557143B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004067814A (en) * | 2002-08-05 | 2004-03-04 | Showa Highpolymer Co Ltd | Polycarboxylic acid resin, polycarboxylic acid resin composition and its cured product |
| JP2007031576A (en) * | 2005-07-27 | 2007-02-08 | Dainippon Ink & Chem Inc | Method for producing branched polyether resin composition and method for producing acid pendant-type branched polyether resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI557143B (en) | 2016-11-11 |
| TW201343690A (en) | 2013-11-01 |
| CN104220478B (en) | 2016-03-02 |
| JPWO2013141117A1 (en) | 2015-08-03 |
| CN104220478A (en) | 2014-12-17 |
| WO2013141117A1 (en) | 2013-09-26 |
| IN2014DN08494A (en) | 2015-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104974594B (en) | The ink composite of a kind of water-soluble solvent, its application and printed circuit board (PCB) | |
| US20030199655A1 (en) | Reactive diluent and curable resin composition | |
| KR102454931B1 (en) | Photocurable resin composition, ink and coating material | |
| EP1505090A1 (en) | Reactive diluent composition and curable resin composition | |
| CN105086604A (en) | Printing ink composition, application thereof and printed circuit board | |
| JP5517112B2 (en) | Photocurable resin composition and its use | |
| JP5495087B2 (en) | Active energy ray curable composition, active energy ray curable coating and active energy ray curable printing ink using the same | |
| JP2008045104A (en) | Active energy ray-curable coating resin composition | |
| JP2011190421A (en) | Active energy ray-curable adhesive composition | |
| JP2017066347A (en) | Curable composition | |
| JP4333100B2 (en) | Active energy ray-curable pressure-sensitive adhesive and pressure-sensitive adhesive sheet | |
| JP2005179511A (en) | Radically polymerizable coating material composition | |
| JP2008045103A (en) | Resin composition for active energy ray-curable ink | |
| JP2016190907A (en) | Photocurable resin composition, ink, and coating material | |
| CN105086605B (en) | A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it | |
| JP4134606B2 (en) | Active energy ray-curable pressure-sensitive adhesive and pressure-sensitive adhesive sheet | |
| JPS63145372A (en) | Actinic radiation curable paint | |
| TW201610028A (en) | Active-energy-ray-curable composition | |
| JP2018178071A (en) | Active energy ray-curable resin composition and cured product thereof | |
| JPH11302562A (en) | Photocurable coating composition | |
| JP2012001671A (en) | Photo- and moisture-curable composition | |
| TWI808944B (en) | Photocurable resin composition, ink and paint | |
| JPWO2015133560A1 (en) | Active energy ray-curable coating agent composition | |
| JP7465398B1 (en) | Solvent-free hard coat resin composition and optical laminate using the same | |
| JP2019151774A (en) | Active energy ray-curable adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140206 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140219 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5495087 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |