WO2015016131A1 - Active energy ray-curable offset ink composition - Google Patents
Active energy ray-curable offset ink composition Download PDFInfo
- Publication number
- WO2015016131A1 WO2015016131A1 PCT/JP2014/069563 JP2014069563W WO2015016131A1 WO 2015016131 A1 WO2015016131 A1 WO 2015016131A1 JP 2014069563 W JP2014069563 W JP 2014069563W WO 2015016131 A1 WO2015016131 A1 WO 2015016131A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active energy
- energy ray
- ink composition
- curable offset
- offset ink
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000003112 inhibitor Substances 0.000 claims abstract description 30
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
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- NPPJLSILDPVHCM-UHFFFAOYSA-N Felbinac ethyl Chemical compound C1=CC(CC(=O)OCC)=CC=C1C1=CC=CC=C1 NPPJLSILDPVHCM-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- VLVZXTNDRFWYLF-UHFFFAOYSA-N [2-ethyl-2-(prop-2-enoyloxymethyl)hexyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CC)(CCCC)COC(=O)C=C VLVZXTNDRFWYLF-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
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- MKSISPKJEMTIGI-LWTKGLMZSA-K aluminum (Z)-oxido-oxidoimino-phenylazanium Chemical compound [Al+3].[O-]\N=[N+](/[O-])c1ccccc1.[O-]\N=[N+](/[O-])c1ccccc1.[O-]\N=[N+](/[O-])c1ccccc1 MKSISPKJEMTIGI-LWTKGLMZSA-K 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- ICQFAQGXJAVDED-UHFFFAOYSA-N benzene-1,4-diol;4-(methylamino)phenol Chemical compound OC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ICQFAQGXJAVDED-UHFFFAOYSA-N 0.000 description 1
- LWGLGSPYKZTZBM-UHFFFAOYSA-N benzenecarbonothioylsulfanyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(=S)SSC(=S)C1=CC=CC=C1 LWGLGSPYKZTZBM-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 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
- 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 1
- 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 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GZCJJOLJSBCUNR-UHFFFAOYSA-N chroman-6-ol Chemical compound O1CCCC2=CC(O)=CC=C21 GZCJJOLJSBCUNR-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229930003836 cresol Natural products 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
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 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
- 239000000839 emulsion Substances 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- HVXYQAREJSKQNE-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide Chemical compound CC(=O)NC1CC(C)(C)NC(C)(C)C1 HVXYQAREJSKQNE-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon 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
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-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
- 150000003672 ureas Chemical class 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 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
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
Definitions
- the present invention relates to an invention of active energy ray-curable offset ink considering safety such as low toxicity for toys and food packaging applications that cure well under active energy ray conditions, and a printed matter thereof.
- Active energy ray curable offset inks are widely used in the field of package printing for food packaging such as toys and paper containers because of the convenience of instantaneous curing characteristics.
- the active energy rays described in the present invention refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- a photopolymerization initiator to the active energy ray-curable composition of the present invention to improve curability.
- a photosensitizer can be further added to improve curability.
- ionizing radiation such as electron beam, ⁇ ray, ⁇ ray, and ⁇ ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer.
- UV rays and electron beams are often used, and in particular, ultraviolet rays are widely used.
- An ultraviolet lamp light source that emits ultraviolet rays is installed inside the printing press, and ink printed on the printing paper passes immediately below the lamp and is instantaneously cured by being irradiated with ultraviolet energy.
- the present invention can be used with or without a photopolymerization initiator or a photosensitizer.
- active energy ray-curable inks tend to thicken after long-term storage, and when the phenomenon becomes excessive, they tend to polymerize (gel). This is because, even in an environment where the active energy rays are not directly applied to the ink, the polymerizable monomer or oligomer in the ink composition generates radicals due to heat, and the polymerization proceeds gradually due to a dark reaction. . Therefore, it is preferable to store the active energy ray-curable ink in a cool and dark place. However, since it is still difficult to avoid the problem of gelation, a polymerization inhibitor is generally used for the purpose of obtaining storage stability (storage stability). It has been added.
- Typical polymerization inhibitors used in active energy ray-curable offset inks include N-nitrosophenylhydroxylamine aluminum salts, especially because they have excellent performance as polymerization inhibitors and improve the storage stability of the ink. Although it has been widely used (see, for example, Patent Document 1), such nitrosamine compounds have been pointed out to be toxic problems such as mutagenicity, and have been improved due to the recent increase in interest in the safety of printing inks. Is desired.
- quinone inhibitors such as hydroquinone and tert-butylhydroquinone, phenothiazine, and the like have been proposed as polymerization inhibitors widely used in the field of active energy ray-curable inks and the same curable inkjet printing inks (for example, Patent Documents 2, 3, and 4) tend to be greatly inferior to nitrosamine compounds in terms of storage stability.
- the present invention is compatible with storage stability while maintaining its safety.
- the problem of the present invention is that it has good curability and low toxicity for toys and food packaging applications, and has improved productivity and storage stability due to excellent curability in offset printing, which hinders coloring as an ink. There is no active energy ray-curable offset ink composition.
- the inventors of the present invention have a polymerization inhibitor having the following specific structure, which has a particularly excellent storage stability even in an active energy ray-curable offset ink composition, and has no concern about toxicity. As a result, the present inventors have found that no coloring occurs.
- the present invention is an active energy ray-curable offset ink composition containing a pigment, a polymerizable monomer, and a polymerization inhibitor composition, and is represented by the general formula (1) as the polymerization inhibitor composition.
- a hindered amine polymerization inhibitor having an oxyl radical structure is contained in an active energy ray-curable offset ink composition in an amount of 0.01 to 0.8% by weight, and Z in the general formula (1) is a hydroxyl group, O—
- An activity characterized by being a methacryloyl group, an optionally substituted vinyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, a halogen atom, an acetamide group, or an acetamidyl group
- An energy ray curable offset ink composition is provided.
- R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R2, R3, and R4 each independently represents an alkyl group having 1 to 6 carbon atoms.
- the active energy ray-curable offset ink composition of the present invention has high curability but is toxic and is not suitable for toys and food packaging, or is inferior in curability to ink compositions with poor storage stability.
- An active energy ray-curable offset ink for toys and food packaging having low storage stability can be obtained.
- the present invention is an active energy ray-curable offset ink composition having 0.01 to 0.8% by weight of a hindered amine polymerization inhibitor having an N-oxyl radical structure having the formula (1) as a constituent.
- Z is a hydroxyl group, an O-methacryloyl group, a vinyl group which may have a substituent, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, halogen, It has an N-oxyl radical structure which is an atom, an acetamide group, or an acetamidyl group.
- R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R2, R3, and R4 each independently have an alkyl group having 1 to 6 carbon atoms.
- Z in the formula (1) is an alkyl group or a cycloalkyl group and has more than 12 carbon atoms, or when R1, R2, R3, or R4 in the formula (1) is an alkyl group and has more than 6 carbon atoms However, it is not preferable because the storage stability performance as an inhibitor is lowered.
- the active energy ray-curable offset ink composition of the present invention is substantially free of volatile components such as water and organic solvents, and is in the state of a composition containing no volatile components, and is a polymerization inhibitor. It is preferable that the amount used be within the range of 0.01 to 0.8% by weight.
- the number of carbon atoms is more preferably 1-6.
- hindered amine polymerization inhibitors having an N-oxyl radical structure having the above formula (1) as a constituent
- 4-acetylamino-2,2,6,6-tetramethylpiperidine wherein Z is an acetamide group -N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl in which Z is a hydroxyl group are preferred, and 4-hydroxy-2,2,6,6- in which Z is a hydroxyl group Tetramethylpiperidine-N-oxyl is more preferable in terms of low toxicity and excellent storage stability.
- polymerization inhibitor compounds examples include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine.
- the active energy ray-curable offset ink composition of the present invention is composed of a binder resin, a monomer, a color pigment, an extender pigment and the like in addition to the polymerization inhibitor, and further includes a photopolymerization initiator and a photosensitizer as necessary. A dispersant or the like may be added.
- a binder resin compound in the active energy ray-curable offset ink composition of the present invention, can be used.
- the binder resin described here refers to all compounds having appropriate pigment affinity and dispersibility, and water resistance and emulsion rheological properties required for offset inks.
- a non-reactive resin Diallyl phthalate resin, epoxy resin, polyurethane resin, poly (meth) acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, etc.
- an epoxy acrylate compound, a urethane acrylate compound, a polyester acrylate compound, or the like having at least one polymerizable group in the resin molecule can be used.
- These binder resin compounds can be used alone or in any case. Use more than one species in combination It may be.
- the polymerizable monomer used as an essential component of the active energy ray-curable offset ink composition of the present invention a monomer compound having a publicly known ethylenic double bond can be used, and a methacrylate monomer is used in combination as appropriate.
- a monomer compound having a publicly known ethylenic double bond can be used, and a methacrylate monomer is used in combination as appropriate.
- a bifunctional or higher functional acrylate monomer which is more reactive than a monofunctional monomer, but depending on the application, adhesion to a printing substrate, flexibility of a cured coating film In order to obtain the necessary physical properties such as, it is possible to use a monofunctional acrylate monomer as appropriate.
- Examples of the monofunctional acrylate monomer include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, octadecyl acrylate, isoamyl acrylate, isodecyl acrylate, isostearyl acrylate, and cyclohexyl.
- bifunctional or higher functional acrylate monomer examples include 1,4-butanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 2 -Methyl-1,8-octanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, tricyclodecane dimethanol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, Dihydric alcohol diacrylates such as dipropylene glycol diacrylate and tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol A trivalent or more polyvalent polyacrylate such as acrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, trimethylolpropane triacrylate, pentaerythri
- an acrylate monomer having two or more functions is generally used as a main monomer.
- an ink composition used in a high-speed offset printer has a highly reactive acrylate monomer having three or more functions.
- the ink jet ink composition is mainly different from the ink-jet ink composition mainly composed of monofunctional and bifunctional monomers in that it is used as a main monomer. Therefore, the risk of occurrence of polymerization solidification (gelation) during storage of the active energy ray-curable offset ink composition is not the ratio of inkjet, but the present invention provides good storage stability to these offset ink compositions.
- Active energy ray-curable composition containing at least 20% by weight of a tetrafunctional or higher acrylate monomer in the composition, or pentafunctional such as dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate, which is particularly highly reactive
- pentafunctional such as dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate, which is particularly highly reactive
- the present invention also works effectively for an active energy ray-curable composition containing the above acrylate monomer in an amount of 10% by weight or more.
- Examples of the pigment used as an essential component of the active energy ray-curable offset ink composition of the present invention include publicly known organic pigments for coloring.
- Organic Pigment Handbook Author: Isao Hashimoto, Publisher: Organic pigments for printing inks, etc., which are listed in "Color Office, first edition 2006”
- soluble azo pigments insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone Pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used. .
- the active energy ray for curing the active energy ray-curable offset ink composition of the present invention is ultraviolet light
- Sensitizers can be widely used.
- Examples of the photopolymerization initiator 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.
- 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 -Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone, 4,4'-diethylaminobenzophenone; -2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators can be used alone or in combination of two or more.
- photosensitizer examples include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. And sulfur compounds. These photosensitizers can be used alone or in combination of two or more.
- photopolymerization initiators and photosensitizers are used in an amount of preferably 0.05 to 20% by weight, more preferably 3 to 15% by weight, based on the total amount of ink.
- the active energy ray for curing the active energy ray-curable ink of the present invention is an ionizing radiation such as an ultraviolet ray, an electron beam, an ⁇ ray, a ⁇ ray, and a ⁇ ray.
- 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.
- the printing substrate used in the printed matter of the present invention is not particularly limited.
- paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, various synthetic papers, polyester resin, acrylic resin, chloride Films or sheets of vinyl resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate,
- Examples include cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
- the binder resin, the polymerizable monomer, the polymerization inhibitor, and other additives are blended in the same manner as the conventional active energy ray-curable ink. It is manufactured by stirring and mixing with a mixer or the like and kneading using a dispersing machine such as a three-roll mill or a bead mill.
- a dispersing machine such as a three-roll mill or a bead mill.
- the active energy ray for curing the ink is ultraviolet rays
- a photopolymerization initiator and a photosensitizer are used and blended and kneaded in the same manner as the above raw materials.
- each polymerization inhibitor was blended into the produced base ink, and after stirring uniformly with a mixer, the kneaded meat was produced again with a three-roll mill. Active energy ray-curable offset inks of Comparative Examples 1 to 15 were produced.
- a DSC measurement sample was prepared by weighing 5 mg of the ink composition in a simple sealed aluminum container (volume: 7.5 microliters) manufactured by Hitachi High-Tech Science Co., Ltd., and sealing with a lid. Using an empty sealed container as a reference, the sample was heated from 30 ° C to 300 ° C for 27 minutes (temperature increase rate 10 ° C / min) in an environment where nitrogen was flowed into the X-DSC7000 measurement chamber. The rising temperature of the DSC exothermic peak of the measurement sample was measured and recorded. Since the polymerization reaction (gelation) starts when the ink composition is heated, the ink composition is measured by comparing the rising temperature (polymerization heat generation temperature) of the DSC exothermic peak with the generated polymerization heat.
- the ink composition was uniformly stretched onto the rubber roll and metal roll of the RI tester using 0.13 ml of ink, and film tack paper (DAITAC UVPET transparent) 25EMH-S, manufactured by DIC), developed to be uniformly applied with a red density of 2.2 (measured with X-Rite SpectroEye densitometer) over an area of approximately 200 cm 2 Was made.
- the RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
- the developed color ink was conditioned at an acceleration voltage of 165 kilovolts, a beam current value of 4.0 milliamperes, an atmospheric oxygen concentration of 300 ppm, and an electron beam dose of 20 kilogrey.
- the layer was cured.
- the cured ink layer was rubbed strongly with a nail (scratch resistance test) to evaluate the EB curability of the ink.
- ⁇ The cured ink layer is not scratched and the curability is good.
- X The cured ink layer is scratched and the curability is poor.
- Tables 1 to 3 are weight% excluding the numerical value of the polymerization heat generation temperature.
- the raw materials and abbreviations shown in Tables 1 to 3 are shown below.
- ⁇ Daiso Dup A diallyl phthalate resin, manufactured by Daiso ⁇ SR355NS: ditrimethylolpropane tetraacrylate, manufactured by Sartomer ⁇ DPHA: dipentaerythritol hexaacrylate, manufactured by Sartomer ⁇ IRGAZIN RULINE L 4025: Pigment Red 264 pigment, manufactured by BASF -CINQUASIA MAGENTA L 4540: 1: 1 mixture of Pigment Violet 19 and Pigment Red 202, manufactured by BASF Corp.-Tansan Magnesium TT: Basic Magnesium Carbonate, manufactured by Naika Shigyo Co., Ltd.
- Solspurs 24000GR Dispersant (polyester resin), Made by Lubrizol [Polymerization inhibitor] Steerer TBH: 2-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. Metoquinone: p-methoxyphenol, manufactured by Seiko Chemical Co., Ltd., Kinopower MNT: 4-methoxy-1-naphthol, manufactured by Kawasaki Kasei Kogyo Co., Ltd., Nonflex Alba: 2 , 5-di-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. ⁇ Hydroquinone: hydroquinone, manufactured by Seiko Chemical Co., Ltd.
- Phenothiazine phenothiazine, manufactured by Seiko Chemical Co., Ltd.
- ⁇ -tocopherol Vitamin E, 2,5,7,8-tetramethyl-2- (4 8,12-trimethyltridecan-1-yl) chroman-6-ol, manufactured by Tokyo Chemical Industry Co., Ltd.
- 4-hydroxy-2 which is a hindered amine polymerization inhibitor having a structure of an N-oxyl radical having the formula (1) as a constituent, is used as a polymerization inhibitor.
- the gelation of the ink which is a necessary characteristic of the present invention, does not occur even after 4 weeks, and heat of polymerization is generated.
- the temperature was as high as 200 ° C. or higher, and it was confirmed that the storage stability was excellent. In addition, good ink curability was obtained.
- a polymerization inhibitor is not blended, or a composition blended with a polymerization inhibitor that does not have the chemical structure represented by the above formula (1) has passed four weeks.
- the active energy ray-curable offset ink composition of the present invention and printed materials using the same are widely used for sanitary, cosmetics and pharmaceutical packaging and filling applications, in addition to toys and food packaging materials that emphasize safety and hygiene. Can be done.
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Abstract
The present invention addresses the problem of providing an active energy ray-curable offset ink composition which has both good curability and low toxicity suitable for use in toys and for food packaging purposes, also has excellent curability in offset printing and therefore has improved productivity and storage stability, and can be colored easily to produce an ink.
An active energy ray-curable offset ink composition characterized in that a hindered amine-type polymerization inhibitor having a N-oxyl radical structure exhibits specifically excellent storage stability in the active energy ray-curable offset ink composition, is free from the concerns of toxicity, and does not undergo discoloration.
Description
本発明は、活性エネルギー線条件下で良好に硬化する玩具及び食品包装用途のための低毒性等安全性に配慮した活性エネルギー線硬化型オフセットインキの発明、並びにその印刷物に関する。
The present invention relates to an invention of active energy ray-curable offset ink considering safety such as low toxicity for toys and food packaging applications that cure well under active energy ray conditions, and a printed matter thereof.
活性エネルギー線硬化型オフセットインキは、瞬間硬化の特性の利便性から、玩具や紙器等の食品包装向けパッケージ印刷の分野で広く使用されている。
Active energy ray curable offset inks are widely used in the field of package printing for food packaging such as toys and paper containers because of the convenience of instantaneous curing characteristics.
本発明で述べる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組成物中に光重合開始剤を添加し、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、特に光重合開始剤や光増感剤を添加する必要はない。印刷分野においては紫外線および電子線が多く用いられており、特に紫外線が広範に利用される。紫外線を放射する紫外線ランプ光源は印刷機内部に設置されており、印刷用紙上に印刷されたインキはランプ直下を通過し、紫外線エネルギーを照射されることによって瞬間的に硬化される。本発明は光重合開始剤や光増感剤の有無に関わらず利用することができる。
The active energy rays described in the present invention refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition 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. There is no need to add a photosensitizer. In the printing field, ultraviolet rays and electron beams are often used, and in particular, ultraviolet rays are widely used. An ultraviolet lamp light source that emits ultraviolet rays is installed inside the printing press, and ink printed on the printing paper passes immediately below the lamp and is instantaneously cured by being irradiated with ultraviolet energy. The present invention can be used with or without a photopolymerization initiator or a photosensitizer.
一方で、活性エネルギー線硬化型インキは長期保存によりインキが増粘し、その現象が過度となる場合には重合固化（ゲル化）してしまう傾向がある。これはインキに上記活性エネルギー線が直接当たらない環境下にあっても、熱によりインキ組成物中の重合性モノマーやオリゴマーがラジカルを発生し、暗反応によって徐々に重合が進行することに起因する。従って活性エネルギー線硬化型インキは冷暗所に保管することが好ましいが、それでもゲル化の問題を回避することは困難であることから、一般に保存安定性（貯蔵安定性）を得る目的で重合禁止剤が添加されている。
On the other hand, active energy ray-curable inks tend to thicken after long-term storage, and when the phenomenon becomes excessive, they tend to polymerize (gel). This is because, even in an environment where the active energy rays are not directly applied to the ink, the polymerizable monomer or oligomer in the ink composition generates radicals due to heat, and the polymerization proceeds gradually due to a dark reaction. . Therefore, it is preferable to store the active energy ray-curable ink in a cool and dark place. However, since it is still difficult to avoid the problem of gelation, a polymerization inhibitor is generally used for the purpose of obtaining storage stability (storage stability). It has been added.
活性エネルギー線硬化型オフセットインキに使用される代表的な重合禁止剤としてはＮ－ニトロソフェニルヒドロキシルアミンアルミニウム塩が挙げられ、特に重合禁止剤としての性能に優れインキの保存安定性を向上させることから広範にわたって利用されてきたが（例えば、特許文献１参照）、このようなニトロソアミン化合物は変異原性等の毒性の問題が指摘されており、昨今の印刷インキの安全性に対する関心の高まりから、改善が要望されている。
Typical polymerization inhibitors used in active energy ray-curable offset inks include N-nitrosophenylhydroxylamine aluminum salts, especially because they have excellent performance as polymerization inhibitors and improve the storage stability of the ink. Although it has been widely used (see, for example, Patent Document 1), such nitrosamine compounds have been pointed out to be toxic problems such as mutagenicity, and have been improved due to the recent increase in interest in the safety of printing inks. Is desired.
更に、活性エネルギー線硬化型インキや同硬化性インクジェット印刷用インクの分野で広範に用いられる重合禁止剤としては、ヒドロキノンやｔｅｒｔ－ブチルハイドロキノン等のキノン系禁止剤やフェノチアジン等が提案されている（例えば、特許文献２、３、４を参照）が保存安定性の点でニトロソアミン化合物に大きく劣る傾向にある。
Furthermore, quinone inhibitors such as hydroquinone and tert-butylhydroquinone, phenothiazine, and the like have been proposed as polymerization inhibitors widely used in the field of active energy ray-curable inks and the same curable inkjet printing inks ( For example, Patent Documents 2, 3, and 4) tend to be greatly inferior to nitrosamine compounds in terms of storage stability.
また、ジメチルジチオカルバミン酸銅等のゴム硫化剤として知られる銅化合物も優れた保存安定性能を示すが（例えば、特許文献５参照）、変異原性を示唆する報告もあり、また強い銅色を呈するため白色や透明の組成物では添加により組成物が銅色に着色されてしまい、利用が制限されてしまう問題があった。
In addition, copper compounds known as rubber sulfiding agents such as copper dimethyldithiocarbamate also exhibit excellent storage stability performance (see, for example, Patent Document 5), but there are reports suggesting mutagenicity and a strong copper color. For this reason, there is a problem in that the use of white or transparent compositions is limited in use because the composition is colored copper.
従って、玩具及び食品包装用途向けの活性エネルギー線硬化型オフセットインキとして、その安全性を保持しつつ、保存安定性を両立させたのが本発明である。
Therefore, as the active energy ray-curable offset ink for toy and food packaging applications, the present invention is compatible with storage stability while maintaining its safety.
本発明の課題は、良好な硬化性及び玩具、食品包装用途のための低毒性を兼ね備えつつ、オフセット印刷における優れた硬化性による生産性向上及び保存安定性を有し、インキとして着色するに支障ない活性エネルギー線硬化型オフセットインキ組成物を提供することにある。
The problem of the present invention is that it has good curability and low toxicity for toys and food packaging applications, and has improved productivity and storage stability due to excellent curability in offset printing, which hinders coloring as an ink. There is no active energy ray-curable offset ink composition.
本発明者らは、下記の特定構造を有する重合禁止剤が、活性エネルギー線硬化型オフセットインキ組成物においても特異的に優れた保存安定性を有しており、かつ毒性懸念がなくインキ組成物への着色も発生しないことを見出し、本発明に至った。
The inventors of the present invention have a polymerization inhibitor having the following specific structure, which has a particularly excellent storage stability even in an active energy ray-curable offset ink composition, and has no concern about toxicity. As a result, the present inventors have found that no coloring occurs.
すなわち本発明は、顔料、重合性モノマー、及び重合禁止剤組成部を含有する活性エネルギー線硬化型オフセットインキ組成物であって、前記重合禁止剤組成物として一般式（１）式で示されるＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤を活性エネルギー線硬化型オフセットインキ組成物中に０．０１～０．８重量％有し、且つ一般式（１）中のＺが水酸基、Ｏ－メタクロイル基、置換基を有してもよいビニル基、炭素数１～１２のアルキル基、炭素数１～１２のシクロアルキル基、ハロゲン原子、アセタミド基、又はアセタミジル基であることを特徴とする活性エネルギー線硬化型オフセットインキ組成物を提供する。
That is, the present invention is an active energy ray-curable offset ink composition containing a pigment, a polymerizable monomer, and a polymerization inhibitor composition, and is represented by the general formula (1) as the polymerization inhibitor composition. A hindered amine polymerization inhibitor having an oxyl radical structure is contained in an active energy ray-curable offset ink composition in an amount of 0.01 to 0.8% by weight, and Z in the general formula (1) is a hydroxyl group, O— An activity characterized by being a methacryloyl group, an optionally substituted vinyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, a halogen atom, an acetamide group, or an acetamidyl group An energy ray curable offset ink composition is provided.
本発明の活性エネルギー線硬化型オフセットインキ組成物により、従来の硬化性は高いものの毒性があり玩具、食品包装に適さない、あるいは保存安定性に劣るインキ組成に対し、硬化性に遜色なく毒性が低く保存安定性を兼ね備えた玩具、食品包装向け活性エネルギー線硬化型オフセットインキを得ることができる。
The active energy ray-curable offset ink composition of the present invention has high curability but is toxic and is not suitable for toys and food packaging, or is inferior in curability to ink compositions with poor storage stability. An active energy ray-curable offset ink for toys and food packaging having low storage stability can be obtained.
本発明は、前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤を０．０１～０．８重量％有する活性エネルギー線硬化型オフセットインキ組成物である。
The present invention is an active energy ray-curable offset ink composition having 0.01 to 0.8% by weight of a hindered amine polymerization inhibitor having an N-oxyl radical structure having the formula (1) as a constituent.
ここで述べる前記（１）式は、Ｚが水酸基、Ｏ－メタクロイル基、置換基を有してもよいビニル基、炭素数１～１２のアルキル基、炭素数１～１２のシクロアルキル基、ハロゲン原子、アセタミド基、又はアセタミジル基であるＮ－オキシルラジカルの構造を有する。但し、上記（１）式において、Ｒ１は、水素原子または炭素数１～６のアルキル基を表し、Ｒ２、Ｒ３、及びＲ４は、それぞれ独立に、炭素数１～６のアルキル基を有する。
In the formula (1) described here, Z is a hydroxyl group, an O-methacryloyl group, a vinyl group which may have a substituent, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, halogen, It has an N-oxyl radical structure which is an atom, an acetamide group, or an acetamidyl group. However, in the formula (1), R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2, R3, and R4 each independently have an alkyl group having 1 to 6 carbon atoms.
上記（１）式におけるＺがアルキル基、シクロアルキル基であり炭素数が１２を超える場合、もしくは上記（１）式におけるＲ１、Ｒ２、Ｒ３、Ｒ４がアルキル基であり炭素数が６を超える場合には禁止剤としての保存安定性能が低下することから好ましくない。
When Z in the formula (1) is an alkyl group or a cycloalkyl group and has more than 12 carbon atoms, or when R1, R2, R3, or R4 in the formula (1) is an alkyl group and has more than 6 carbon atoms However, it is not preferable because the storage stability performance as an inhibitor is lowered.
前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤の含有量が０．０１重量％を下回ると保存安定性の明確な改善効果が得られず、また０．８重量％を上回ると活性エネルギー線照射による硬化後の皮膜の耐スクラッチ（傷）性が低下する傾向が見られる。また本発明の活性エネルギー線硬化型オフセットインキ組成物は実質的に水や有機溶剤等の揮発性成分を含有しないことを特徴としており、揮発成分を含まない組成物の状態にあって重合禁止剤の使用量が０．０１～０．８重量％の範囲に収まることが好ましい。
When the content of the hindered amine polymerization inhibitor having the structure of the N-oxyl radical having the structure of the formula (1) is less than 0.01% by weight, a clear improvement effect of storage stability cannot be obtained. If it exceeds 0.8% by weight, the scratch resistance of the film after curing by irradiation with active energy rays tends to decrease. In addition, the active energy ray-curable offset ink composition of the present invention is substantially free of volatile components such as water and organic solvents, and is in the state of a composition containing no volatile components, and is a polymerization inhibitor. It is preferable that the amount used be within the range of 0.01 to 0.8% by weight.
前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤において、Ｚがアルキル基、又はシクロアルキル基の場合、炭素数１～６がより好ましい。
In the hindered amine polymerization inhibitor having an N-oxyl radical structure having the formula (1) as a constituent, when Z is an alkyl group or a cycloalkyl group, the number of carbon atoms is more preferably 1-6.
また、前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤の中でも、Ｚがアセタミド基である４－アセチルアミノ－２，２，６,６－テトラメチルピペリジン－Ｎ－オキシル、及びＺが水酸基である４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルが好ましく、Ｚが水酸基である４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルが低毒性、優れた保存安定性の点でより好ましい。
Among the hindered amine polymerization inhibitors having an N-oxyl radical structure having the above formula (1) as a constituent, 4-acetylamino-2,2,6,6-tetramethylpiperidine wherein Z is an acetamide group -N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl in which Z is a hydroxyl group are preferred, and 4-hydroxy-2,2,6,6- in which Z is a hydroxyl group Tetramethylpiperidine-N-oxyl is more preferable in terms of low toxicity and excellent storage stability.
重合禁止剤化合物としては、前記したものも含め（アルキル）フェノール、ハイドロキノン、カテコール、レゾルシン、ｐ－メトキシフェノール、ｔ－ブチルカテコール、t－ブチルハイドロキノン、ピロガロール、１，１－ピクリルヒドラジル、フェノチアジン、ｐ－ベンゾキノン、ニトロソベンゼン、２，５－ジ－ｔ－ブチル－ｐ－ベンゾキノン、ジチオベンゾイルジスルフィド、ピクリン酸、クペロン、アルミニウム－Ｎ－ニトロソフェニルヒドロキシルアミン、トリ－ｐ－ニトロフェニルメチル、Ｎ－（３－オキシアニリノ－１，３－ジメチルブチリデン）アニリンオキシド、ジブチルクレゾール、シクロヘキサノンオキシムクレゾール、グアヤコール、ｏ－イソプロピルフェノール、ブチラルドキシム、メチルエチルケトキシム、シクロヘキサノンオキシム等の化合物が例示されるが、本発明で述べる前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤が、保存安定性や安全性、組成物を着色しない点において特に優れている。
Examples of the polymerization inhibitor compounds include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine. P-benzoquinone, nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum-N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methylethylketoxime, Compounds such as cyclohexanone oxime are exemplified, but a hindered amine polymerization inhibitor having an N-oxyl radical structure having the above-described formula (1) described in the present invention as a constituent, has storage stability, safety, and composition. It is particularly excellent in that it is not colored.
本発明の活性エネルギー線硬化型オフセットインキ組成物は、前記重合禁止剤に加え、バインダー樹脂、モノマー、着色顔料、体質顔料等で構成され、更に必要に応じて光重合開始剤、光増感剤、分散剤等を添加してもよい。
The active energy ray-curable offset ink composition of the present invention is composed of a binder resin, a monomer, a color pigment, an extender pigment and the like in addition to the polymerization inhibitor, and further includes a photopolymerization initiator and a photosensitizer as necessary. A dispersant or the like may be added.
本発明の活性エネルギー線硬化型オフセットインキ組成物にはバインダー樹脂化合物を利用することができる。ここで述べるバインダー樹脂とは、適切な顔料親和性と分散性を有し、またオフセットインキに必要とされる耐水性や乳化レオロジー特性を有する化合物全般を示しており、例えば非反応性樹脂としては、ジアリルフタレート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリ（メタ）アクリル酸エステル、セルロース誘導体、塩化ビニルー酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ブタジエンーアクリルニトリル共重合体等を挙げることができ、または樹脂分子中に少なくとも１つ以上の重合性基を有するエポキシアクリレート化合物、ウレタンアクリレート化合物、ポリエステルアクリレート化合物等を用いることもでき、これらバインダー樹脂化合物は、単独で使用しても、いずれか１種以上を組合せて使用してもよい。
In the active energy ray-curable offset ink composition of the present invention, a binder resin compound can be used. The binder resin described here refers to all compounds having appropriate pigment affinity and dispersibility, and water resistance and emulsion rheological properties required for offset inks. For example, as a non-reactive resin, , Diallyl phthalate resin, epoxy resin, polyurethane resin, poly (meth) acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, etc. Alternatively, an epoxy acrylate compound, a urethane acrylate compound, a polyester acrylate compound, or the like having at least one polymerizable group in the resin molecule can be used. These binder resin compounds can be used alone or in any case. Use more than one species in combination It may be.
本発明の活性エネルギー線硬化型オフセットインキ組成物の必須構成成分として用いる重合性モノマーとしては、公知公用のエチレン性二重結合を有するモノマー化合物を利用することが可能であり、メタクリレートモノマーを適宜併用することも可能であるが、本発明においてはより硬化性の優れるアクリレートモノマーを主モノマーとして用いることが好ましい。またオフセットインキ組成物においては、単官能モノマーよりも、より反応性の高い２官能以上のアクリレートモノマーを用いることが好ましいが、用途に応じて印刷基材への接着性、硬化塗膜の柔軟性等の必要物性を得る為に、適宜単官能アクリレートモノマーを併用することが可能である。
As the polymerizable monomer used as an essential component of the active energy ray-curable offset ink composition of the present invention, a monomer compound having a publicly known ethylenic double bond can be used, and a methacrylate monomer is used in combination as appropriate. However, in the present invention, it is preferable to use an acrylate monomer having better curability as the main monomer. In addition, in the offset ink composition, it is preferable to use a bifunctional or higher functional acrylate monomer, which is more reactive than a monofunctional monomer, but depending on the application, adhesion to a printing substrate, flexibility of a cured coating film In order to obtain the necessary physical properties such as, it is possible to use a monofunctional acrylate monomer as appropriate.
前記単官能アクリレートモノマーとしては、例えば、エチルアクリレート、ブチルアクリレート、２－エチルヘキシルアクリレート、ノニルアクリレート、ラウリルアクリレート、トリデシルアクリレート、ヘキサデシルアクリレート、オクタデシルアクリレート、イソアミルアクリレート、イソデシルアクリレート、イソステアリルアクリレート、シクロヘキシルアクリレート、ベンジルアクリレート、メトキシエチルアクリレート、ブトキシエチルアクリレート、フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、ノニルフェノキシエチルアクリレート、テトラヒドロフルフリルアクリレート、グリシジルアクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシー３－フェノキシプロピルアクリレート、３－クロロ－２－ヒドロキシプロピルアクリレート、ジエチルアミノエチルアクリレート、ノニルフェノキシエチルテトラヒドロフルフリルアクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニロキシエチルアクリレート等が挙げられる。
Examples of the monofunctional acrylate monomer include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, octadecyl acrylate, isoamyl acrylate, isodecyl acrylate, isostearyl acrylate, and cyclohexyl. Acrylate, benzyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate Lilate, 3-chloro-2-hydroxypropyl acrylate, diethylaminoethyl acrylate, nonylphenoxyethyl tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxy ethyl acrylate, etc. Is mentioned.
前記２官能以上のアクリレートモノマーとしては、例えば、１，４－ブタンジオールジアクリレート、３－メチル－１，５－ペンタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、２－メチル－１，８－オクタンジオールジアクリレート、２－ブチルー２－エチルー１，３－プロパンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート等の２価アルコールのジアクリレート、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートのジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールのポリアクリレート等の３価以上の多価アルコールのポリアクリレート、ネオペンチルグリコール１モルに２モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジアクリレート、グリセリン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのトリアクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジ又はトリアクリレート、ビスフェノールＡ１モルに２モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジアクリレート等のポリオキシアルキレンポリオールのポリアクリレート等が挙げられる。
Examples of the bifunctional or higher functional acrylate monomer include 1,4-butanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 2 -Methyl-1,8-octanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, tricyclodecane dimethanol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, Dihydric alcohol diacrylates such as dipropylene glycol diacrylate and tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol A trivalent or more polyvalent polyacrylate such as acrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate Diacrylate of a diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of polyhydric alcohol, 1 mol of neopentyl glycol, obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin Triol triacrylate, 3 moles of ethylene oxide or propylene oxide per mole of trimethylolpropane It added to triol di- or tri-acrylates obtained, polyacrylate polyoxyalkylene polyols and di acrylate of a diol obtained by adding 2 moles or more of ethylene oxide or propylene oxide to bisphenol A1 molar and the like.
活性エネルギー線硬化型オフセットインキ組成物においては、一般に２官能以上のアクリレートモノマーが主モノマーとして用いられ、特に高速のオフセット印刷機において利用されるインキ組成物は３官能以上の高反応性アクリレートモノマーが主モノマーとして用いられる点において、単官能および２官能モノマーを中心に構成されるインクジェットインク組成物と大きく異なっている。従って活性エネルギー線硬化型オフセットインキ組成物の保存時における重合固化（ゲル化）の発生リスクはインクジェットの比ではないが、本発明はこれらオフセットインキ組成物に対しても良好な保存安定性を付与することができ、４官能以上のアクリレートモノマーを組成物中に２０重量％以上含む活性エネルギー線硬化型組成物や、特に反応性の高いジペンタエリスリトールペンタアクリレートもしくはジペンタエリスリトールヘキサアクリレート等の５官能以上のアクリレートモノマーを組成物中に１０重量％以上含む活性エネルギー線硬化型組成物に関しても、本発明は有効に作用する。
In the active energy ray-curable offset ink composition, an acrylate monomer having two or more functions is generally used as a main monomer. In particular, an ink composition used in a high-speed offset printer has a highly reactive acrylate monomer having three or more functions. The ink jet ink composition is mainly different from the ink-jet ink composition mainly composed of monofunctional and bifunctional monomers in that it is used as a main monomer. Therefore, the risk of occurrence of polymerization solidification (gelation) during storage of the active energy ray-curable offset ink composition is not the ratio of inkjet, but the present invention provides good storage stability to these offset ink compositions. Active energy ray-curable composition containing at least 20% by weight of a tetrafunctional or higher acrylate monomer in the composition, or pentafunctional such as dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate, which is particularly highly reactive The present invention also works effectively for an active energy ray-curable composition containing the above acrylate monomer in an amount of 10% by weight or more.
本発明の活性エネルギー線硬化型オフセットインキ組成物の必須構成成分として使用する顔料としては、公知公用の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。
Examples of the pigment used as an essential component of the active energy ray-curable offset ink composition of the present invention include publicly known organic pigments for coloring. For example, “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Organic pigments for printing inks, etc., which are listed in "Color Office, first edition 2006"), soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone Pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used. .
本発明の活性エネルギー線硬化型オフセットインキ組成物を硬化させる活性エネルギー線が紫外線である場合には光重合開始剤や光増感剤を用いることが好ましく、一般的な光重合開始剤および光増感剤を広く利用することができる。
When the active energy ray for curing the active energy ray-curable offset ink composition of the present invention is ultraviolet light, it is preferable to use a photopolymerization initiator or a photosensitizer. Sensitizers can be widely used.
前記光重合開始剤としては、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 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 compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.
一方、水素引き抜き型光重合開始剤としては、例えば、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等のチオキサントン系化合物；ミヒラ－ケトン、４，４’－ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、カンファーキノン等が挙げられる。これらの光重合開始剤は、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 -Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone, 4,4'-diethylaminobenzophenone; -2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators 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。これらの光増感剤は、単独で用いることも、２種以上を併用することもできる。
Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. And sulfur compounds. These photosensitizers can be used alone or in combination of two or more.
これらの光重合開始剤及び光増感剤の使用量は、インキ全量に対し、各々０．０５～２０重量％が好ましく、３～１５重量％がより好ましい。
These photopolymerization initiators and photosensitizers are used in an amount of preferably 0.05 to 20% by weight, more preferably 3 to 15% by weight, based on the total amount of ink.
本発明の活性エネルギー線硬化性インキ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 ink of the present invention is an ionizing radiation such as an ultraviolet ray, an electron beam, an α ray, a β ray, and a γ ray. 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.
本発明の印刷物で使用する印刷基材としては、特に限定は無く、例えば、上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙、各種合成紙、ポリエステル樹脂、アクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリアクリロニトリル、エチレン酢酸ビニル共重合体、エチレンビニルアルコール共重合体、エチレンメタクリル酸共重合体、ナイロン、ポリ乳酸、ポリカーボネート等のフィルム又はシート、セロファン、アルミニウムフォイル、その他従来から印刷基材として使用されている各種基材を挙げることが出来る。
The printing substrate used in the printed matter of the present invention is not particularly limited. For example, paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, various synthetic papers, polyester resin, acrylic resin, chloride Films or sheets of vinyl resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate, Examples include cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
本発明で述べる活性エネルギー線硬化型オフセット印刷インキ組成物の製造は、従来の活性エネルギー線硬化型インキと同様に、前記バインダー樹脂、重合性モノマー、重合禁止剤、その他添加剤等を配合してミキサー等で撹拌混合し、三本ロールミル、ビーズミル等の分散機を用いて練肉することで製造される。インキを硬化させる活性エネルギー線が紫外線である場合は、光重合開始剤、光増感剤を用い、上記原料と同様に配合し練肉する。
In the production of the active energy ray-curable offset printing ink composition described in the present invention, the binder resin, the polymerizable monomer, the polymerization inhibitor, and other additives are blended in the same manner as the conventional active energy ray-curable ink. It is manufactured by stirring and mixing with a mixer or the like and kneading using a dispersing machine such as a three-roll mill or a bead mill. When the active energy ray for curing the ink is ultraviolet rays, a photopolymerization initiator and a photosensitizer are used and blended and kneaded in the same manner as the above raw materials.
以下、実施例によって本発明を具体的に説明する。
Hereinafter, the present invention will be specifically described with reference to examples.
〔インキ組成物の製造方法〕
まず表１に示す組成に従って原料を配合し、ミキサーで均一に撹拌した後に三本ロールミルにて練肉製造することでベースインキ（製造例１）を製造した。 [Method for producing ink composition]
First, the raw materials were blended according to the composition shown in Table 1, and after stirring uniformly with a mixer, the base ink (Manufacturing Example 1) was manufactured by producing kneaded meat with a three-roll mill.
まず表１に示す組成に従って原料を配合し、ミキサーで均一に撹拌した後に三本ロールミルにて練肉製造することでベースインキ（製造例１）を製造した。 [Method for producing ink composition]
First, the raw materials were blended according to the composition shown in Table 1, and after stirring uniformly with a mixer, the base ink (Manufacturing Example 1) was manufactured by producing kneaded meat with a three-roll mill.
その後、表２、表３に示す組成に従って、製造したベースインキに各重合禁止剤を配合し、ミキサーで均一に撹拌した後に再度三本ロールミルにて練肉製造することで実施例１及び２、比較例１～１５の活性エネルギー線硬化型オフセットインキを製造した。
Then, according to the composition shown in Table 2 and Table 3, each polymerization inhibitor was blended into the produced base ink, and after stirring uniformly with a mixer, the kneaded meat was produced again with a three-roll mill. Active energy ray-curable offset inks of Comparative Examples 1 to 15 were produced.
〔インキ組成物の評価方法１：ゲル化試験〕
製造したインキ組成物３０ｇを容積５０ミリリットルのアルミニウム製金属容器に投入し、蓋をした状態で、６０℃に保たれたオーブン内部にて保管し、２週間後、４週間後のインキ組成物の状態を、金属スパチュラを容器内部の組成物に差し込むことで指触によりゲル化の有無を判定した。 [Evaluation method 1 of ink composition: gelation test]
30 g of the manufactured ink composition was put into an aluminum metal container having a volume of 50 ml, stored in an oven kept at 60 ° C. with a lid, and after 2 weeks and 4 weeks, The presence or absence of gelation was determined by touching the state by inserting a metal spatula into the composition inside the container.
製造したインキ組成物３０ｇを容積５０ミリリットルのアルミニウム製金属容器に投入し、蓋をした状態で、６０℃に保たれたオーブン内部にて保管し、２週間後、４週間後のインキ組成物の状態を、金属スパチュラを容器内部の組成物に差し込むことで指触によりゲル化の有無を判定した。 [Evaluation method 1 of ink composition: gelation test]
30 g of the manufactured ink composition was put into an aluminum metal container having a volume of 50 ml, stored in an oven kept at 60 ° C. with a lid, and after 2 weeks and 4 weeks, The presence or absence of gelation was determined by touching the state by inserting a metal spatula into the composition inside the container.
○：インキ組成物にゲル化が確認されず、保存安定性は良好である
×：インキ組成物にゲル化が確認され、保存安定性は不良である
〔インキ組成物の評価方法２：重合熱発生温度〕
製造した活性エネルギー線硬化型オフセットインキ組成物に関して、日立ハイテクサイエンス社製Ｘ－ＤＳＣ７０００を用いてＤＳＣ測定（示差走査熱量測定）を実施することで、保存安定性を評価した。 ○: No gelation was confirmed in the ink composition, and the storage stability was good. X: Gelation was confirmed in the ink composition, and the storage stability was poor. [Evaluation method 2 of ink composition: heat of polymerization Generation temperature)
With respect to the produced active energy ray-curable offset ink composition, storage stability was evaluated by performing DSC measurement (differential scanning calorimetry) using X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.
×：インキ組成物にゲル化が確認され、保存安定性は不良である
〔インキ組成物の評価方法２：重合熱発生温度〕
製造した活性エネルギー線硬化型オフセットインキ組成物に関して、日立ハイテクサイエンス社製Ｘ－ＤＳＣ７０００を用いてＤＳＣ測定（示差走査熱量測定）を実施することで、保存安定性を評価した。 ○: No gelation was confirmed in the ink composition, and the storage stability was good. X: Gelation was confirmed in the ink composition, and the storage stability was poor. [Evaluation method 2 of ink composition: heat of polymerization Generation temperature)
With respect to the produced active energy ray-curable offset ink composition, storage stability was evaluated by performing DSC measurement (differential scanning calorimetry) using X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.
日立ハイテクサイエンス社製の簡易密封アルミ容器（容量７．５マイクロリットル）内にインキ組成物５ミリグラムを秤量し、蓋をして密閉することでＤＳＣ測定サンプルを用意した。リファレンスとして空の密閉容器を用い、Ｘ－ＤＳＣ７０００の測定チャンバー内に窒素をフローした環境において、測定サンプルを３０℃から３００℃まで２７分間（昇温速度１０℃／分）をかけて昇温し、測定サンプルのＤＳＣ発熱ピークの立ち上がり温度を測定し記録した。インキ組成物は加温されることにより重合反応（ゲル化）が開始する為、発生する重合熱に伴うＤＳＣ発熱ピークの立ち上がり温度（重合熱発生温度）を測定し比較することで、インキ組成物の保存安定性の優劣を評価することが可能である。従って重合熱発生温度が高いほど組成物の保存安定性が優れている。
〔インキ組成物の評価方法３：ＥＢ硬化性〕
製造したインキ組成物を用いて展色物を作製し、電子線（ＥＢ）を照射して硬化させた後に硬化性の評価を実施した。 A DSC measurement sample was prepared by weighing 5 mg of the ink composition in a simple sealed aluminum container (volume: 7.5 microliters) manufactured by Hitachi High-Tech Science Co., Ltd., and sealing with a lid. Using an empty sealed container as a reference, the sample was heated from 30 ° C to 300 ° C for 27 minutes (temperature increase rate 10 ° C / min) in an environment where nitrogen was flowed into the X-DSC7000 measurement chamber. The rising temperature of the DSC exothermic peak of the measurement sample was measured and recorded. Since the polymerization reaction (gelation) starts when the ink composition is heated, the ink composition is measured by comparing the rising temperature (polymerization heat generation temperature) of the DSC exothermic peak with the generated polymerization heat. It is possible to evaluate the superiority or inferiority of storage stability. Therefore, the higher the heat generation temperature for polymerization, the better the storage stability of the composition.
[Evaluation method 3 of ink composition: EB curability]
A color-developed product was prepared using the manufactured ink composition, and cured by irradiation with an electron beam (EB), and then evaluated for curability.
〔インキ組成物の評価方法３：ＥＢ硬化性〕
製造したインキ組成物を用いて展色物を作製し、電子線（ＥＢ）を照射して硬化させた後に硬化性の評価を実施した。 A DSC measurement sample was prepared by weighing 5 mg of the ink composition in a simple sealed aluminum container (volume: 7.5 microliters) manufactured by Hitachi High-Tech Science Co., Ltd., and sealing with a lid. Using an empty sealed container as a reference, the sample was heated from 30 ° C to 300 ° C for 27 minutes (temperature increase rate 10 ° C / min) in an environment where nitrogen was flowed into the X-DSC7000 measurement chamber. The rising temperature of the DSC exothermic peak of the measurement sample was measured and recorded. Since the polymerization reaction (gelation) starts when the ink composition is heated, the ink composition is measured by comparing the rising temperature (polymerization heat generation temperature) of the DSC exothermic peak with the generated polymerization heat. It is possible to evaluate the superiority or inferiority of storage stability. Therefore, the higher the heat generation temperature for polymerization, the better the storage stability of the composition.
[Evaluation method 3 of ink composition: EB curability]
A color-developed product was prepared using the manufactured ink composition, and cured by irradiation with an electron beam (EB), and then evaluated for curability.
インキ組成物を、簡易展色機（ＲＩテスター、豊栄精工社製）を用い、インキ０．１３ｍｌを使用して、ＲＩテスターのゴムロール及び金属ロール上に均一に引き伸ばし、フィルムタック紙（ＤＡＩＴＡＣ ＵＶＰＥＴ透明２５ＥＭＨ－Ｓ、ＤＩＣ社製）の表面に、およそ２００ｃｍ２の面積にわたって紅濃度２．２（Ｘ－Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）で均一に塗布されるように展色し、展色物を作製した。なおＲＩテスターとは、紙やフィルムにインキを展色する試験機であり、インキの転移量や印圧を調整することが可能である。
Using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.), the ink composition was uniformly stretched onto the rubber roll and metal roll of the RI tester using 0.13 ml of ink, and film tack paper (DAITAC UVPET transparent) 25EMH-S, manufactured by DIC), developed to be uniformly applied with a red density of 2.2 (measured with X-Rite SpectroEye densitometer) over an area of approximately 200 cm 2 Was made. The RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
その後、展色物を標準ＥＢ実験機（アイエレクトロンビーム社製）を用いて、加速電圧１６５キロボルト、ビーム電流値４．０ミリアンペア、雰囲気酸素濃度３００ｐｐｍ、電子線照射量線量２０キログレイの条件においてインキ層を硬化させた。
After that, using a standard EB experimental machine (manufactured by Eye Electron Beam Co., Ltd.), the developed color ink was conditioned at an acceleration voltage of 165 kilovolts, a beam current value of 4.0 milliamperes, an atmospheric oxygen concentration of 300 ppm, and an electron beam dose of 20 kilogrey. The layer was cured.
硬化直後に硬化インキ層を爪で強く擦ることにより（耐スクラッチ試験）、インキのＥＢ硬化性を評価した。
Immediately after curing, the cured ink layer was rubbed strongly with a nail (scratch resistance test) to evaluate the EB curability of the ink.
○：硬化インキ層に傷は付かず、硬化性は良好である
×：硬化インキ層に傷が付き、硬化性は不良である
○: The cured ink layer is not scratched and the curability is good. X: The cured ink layer is scratched and the curability is poor.
×：硬化インキ層に傷が付き、硬化性は不良である
○: The cured ink layer is not scratched and the curability is good. X: The cured ink layer is scratched and the curability is poor.
表１～３中の数値は、重合熱発生温度の数値を除いて重量％である。
表１～３に示す諸原料及び略を以下に示す。
・ダイソーダップＡ：ジアリルフタレート樹脂、ダイソー社製
・ＳＲ３５５ＮＳ：ジトリメチロールプロパンテトラアクリレート、サートマー社製
・ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート、サートマー社製
・ＩＲＧＡＺＩＮ ＲＵＢＩＮＥ Ｌ ４０２５：ピグメントレッド２６４顔料、ＢＡＳＦ社製
・ＣＩＮＱＵＡＳＩＡ ＭＡＧＥＮＴＡ Ｌ ４５４０：ピグメントバイオレット１９とピグメントレッド２０２の１：１混合物、ＢＡＳＦ社製
・タンサンマグネシウムＴＴ：塩基性炭酸マグネシウム、ナイカイ塩業社製
・ソルスパ－ズ ２４０００ＧＲ：分散剤（ポリエステル樹脂）、ルーブリゾール社製
[重合禁止剤]
・ステアラーＴＢＨ：２－ｔｅｒｔ－ブチルヒドロキノン、精工化学社製
・メトキノン：ｐ－メトキシフェノール、精工化学社製
・キノパワーＭＮＴ：４－メトキシ－１－ナフトール、川崎化成工業社製
・ノンフレックスアルバ：２，５－ジ－ｔｅｒｔ－ブチルヒドロキノン、精工化学社製
・ハイドロキノン：ヒドロキノン、精工化学社製
・フェノチアジン：フェノチアジン、精工化学社製
・アデカスタブＬＡ－５２：ビス（１，２，２，６，６－ペンタメチルピペリジン－４－イル）＝３，４－ビス｛［（１，２，２，６，６－ペンタメチルピペリジン－４－イル)オキシ]カルボニル｝ヘキサンジオアート、ＡＤＥＫＡ社製
・アデカスタブＬＡ－８２：１，２，２，６，６－ペンタメチル－４－ピペリジル＝メタクリラート、ＡＤＥＫＡ社製
・アデカスタブＬＡ－７ＲＤ：４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシル、ＡＤＥＫＡ社製
・アデカスタブＬＡ－８１：炭酸＝ビス（２，２，６，６－テトラメチル－１－ウンデシルオキシピペリジン－４－イル）、ＡＤＥＫＡ社製
・チヌビン１２３：デカン二酸ビス［２，２，６，６－テトラメチル－１－（オクチルオキシ）ピペリジン－４－イル］、ＢＡＳＦ社製
・オゾノン３５：Ｎ－１－メチルヘプチル－Ｎ’－フェニル－ｐ－フェニレンジアミン、精工化学社製
・α-トコフェロール：ビタミンＥ、２，５，７，８－テトラメチル－２－（４，８，１２－トリメチルトリデカン－１－イル）クロマン－６－オール、東京化成工業社製
実施例に述べる活性エネルギー線硬化型オフセットインキ組成物では、重合禁止剤として前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤である４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルを前記の重量％の範囲で配合することにより、本願発明の必要特性であるインキのゲル化は４週間経過時点でも発生せず、重合熱発生温度も２００℃以上と高く、保存安定性に優れることを確認した。また良好なインキ硬化性が得られた。 The numerical values in Tables 1 to 3 are weight% excluding the numerical value of the polymerization heat generation temperature.
The raw materials and abbreviations shown in Tables 1 to 3 are shown below.
・ Daiso Dup A: diallyl phthalate resin, manufactured by Daiso ・ SR355NS: ditrimethylolpropane tetraacrylate, manufactured by Sartomer ・ DPHA: dipentaerythritol hexaacrylate, manufactured by Sartomer ・ IRGAZIN RULINE L 4025: Pigment Red 264 pigment, manufactured by BASF -CINQUASIA MAGENTA L 4540: 1: 1 mixture of Pigment Violet 19 and Pigment Red 202, manufactured by BASF Corp.-Tansan Magnesium TT: Basic Magnesium Carbonate, manufactured by Naika Shigyo Co., Ltd. Solspurs 24000GR: Dispersant (polyester resin), Made by Lubrizol
[Polymerization inhibitor]
Steerer TBH: 2-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. Metoquinone: p-methoxyphenol, manufactured by Seiko Chemical Co., Ltd., Kinopower MNT: 4-methoxy-1-naphthol, manufactured by Kawasaki Kasei Kogyo Co., Ltd., Nonflex Alba: 2 , 5-di-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. ・ Hydroquinone: hydroquinone, manufactured by Seiko Chemical Co., Ltd. ・ Phenothiazine: phenothiazine, manufactured by Seiko Chemical Co., Ltd. ・ Adeka Stub LA-52: Bis (1,2,2,6,6- Pentamethylpiperidin-4-yl) = 3,4-bis {[(1,2,2,6,6-pentamethylpiperidin-4-yl) oxy] carbonyl} hexane geoate, ADEKA, ADK STAB LA- 82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, ADEKA・ Adekastab LA-7RD: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, manufactured by ADEKA ・ Adekastab LA-81: Carbonic acid = bis (2,2,6,6-tetramethyl- 1-undecyloxypiperidin-4-yl), manufactured by ADEKA, Tinuvin 123: bis [2,2,6,6-tetramethyl-1- (octyloxy) piperidin-4-yl] decanedioate, BASF・ Ozonon 35: N-1-methylheptyl-N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd. α-tocopherol: Vitamin E, 2,5,7,8-tetramethyl-2- (4 8,12-trimethyltridecan-1-yl) chroman-6-ol, manufactured by Tokyo Chemical Industry Co., Ltd.
In the active energy ray-curable offset ink composition described in the examples, 4-hydroxy-2, which is a hindered amine polymerization inhibitor having a structure of an N-oxyl radical having the formula (1) as a constituent, is used as a polymerization inhibitor. By blending 2,6,6-tetramethylpiperidine-N-oxyl in the above weight% range, the gelation of the ink, which is a necessary characteristic of the present invention, does not occur even after 4 weeks, and heat of polymerization is generated. The temperature was as high as 200 ° C. or higher, and it was confirmed that the storage stability was excellent. In addition, good ink curability was obtained.
表１～３に示す諸原料及び略を以下に示す。
・ダイソーダップＡ：ジアリルフタレート樹脂、ダイソー社製
・ＳＲ３５５ＮＳ：ジトリメチロールプロパンテトラアクリレート、サートマー社製
・ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート、サートマー社製
・ＩＲＧＡＺＩＮ ＲＵＢＩＮＥ Ｌ ４０２５：ピグメントレッド２６４顔料、ＢＡＳＦ社製
・ＣＩＮＱＵＡＳＩＡ ＭＡＧＥＮＴＡ Ｌ ４５４０：ピグメントバイオレット１９とピグメントレッド２０２の１：１混合物、ＢＡＳＦ社製
・タンサンマグネシウムＴＴ：塩基性炭酸マグネシウム、ナイカイ塩業社製
・ソルスパ－ズ ２４０００ＧＲ：分散剤（ポリエステル樹脂）、ルーブリゾール社製
[重合禁止剤]
・ステアラーＴＢＨ：２－ｔｅｒｔ－ブチルヒドロキノン、精工化学社製
・メトキノン：ｐ－メトキシフェノール、精工化学社製
・キノパワーＭＮＴ：４－メトキシ－１－ナフトール、川崎化成工業社製
・ノンフレックスアルバ：２，５－ジ－ｔｅｒｔ－ブチルヒドロキノン、精工化学社製
・ハイドロキノン：ヒドロキノン、精工化学社製
・フェノチアジン：フェノチアジン、精工化学社製
・アデカスタブＬＡ－５２：ビス（１，２，２，６，６－ペンタメチルピペリジン－４－イル）＝３，４－ビス｛［（１，２，２，６，６－ペンタメチルピペリジン－４－イル)オキシ]カルボニル｝ヘキサンジオアート、ＡＤＥＫＡ社製
・アデカスタブＬＡ－８２：１，２，２，６，６－ペンタメチル－４－ピペリジル＝メタクリラート、ＡＤＥＫＡ社製
・アデカスタブＬＡ－７ＲＤ：４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシル、ＡＤＥＫＡ社製
・アデカスタブＬＡ－８１：炭酸＝ビス（２，２，６，６－テトラメチル－１－ウンデシルオキシピペリジン－４－イル）、ＡＤＥＫＡ社製
・チヌビン１２３：デカン二酸ビス［２，２，６，６－テトラメチル－１－（オクチルオキシ）ピペリジン－４－イル］、ＢＡＳＦ社製
・オゾノン３５：Ｎ－１－メチルヘプチル－Ｎ’－フェニル－ｐ－フェニレンジアミン、精工化学社製
・α-トコフェロール：ビタミンＥ、２，５，７，８－テトラメチル－２－（４，８，１２－トリメチルトリデカン－１－イル）クロマン－６－オール、東京化成工業社製
実施例に述べる活性エネルギー線硬化型オフセットインキ組成物では、重合禁止剤として前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤である４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルを前記の重量％の範囲で配合することにより、本願発明の必要特性であるインキのゲル化は４週間経過時点でも発生せず、重合熱発生温度も２００℃以上と高く、保存安定性に優れることを確認した。また良好なインキ硬化性が得られた。 The numerical values in Tables 1 to 3 are weight% excluding the numerical value of the polymerization heat generation temperature.
The raw materials and abbreviations shown in Tables 1 to 3 are shown below.
・ Daiso Dup A: diallyl phthalate resin, manufactured by Daiso ・ SR355NS: ditrimethylolpropane tetraacrylate, manufactured by Sartomer ・ DPHA: dipentaerythritol hexaacrylate, manufactured by Sartomer ・ IRGAZIN RULINE L 4025: Pigment Red 264 pigment, manufactured by BASF -CINQUASIA MAGENTA L 4540: 1: 1 mixture of Pigment Violet 19 and Pigment Red 202, manufactured by BASF Corp.-Tansan Magnesium TT: Basic Magnesium Carbonate, manufactured by Naika Shigyo Co., Ltd. Solspurs 24000GR: Dispersant (polyester resin), Made by Lubrizol
[Polymerization inhibitor]
Steerer TBH: 2-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. Metoquinone: p-methoxyphenol, manufactured by Seiko Chemical Co., Ltd., Kinopower MNT: 4-methoxy-1-naphthol, manufactured by Kawasaki Kasei Kogyo Co., Ltd., Nonflex Alba: 2 , 5-di-tert-butylhydroquinone, manufactured by Seiko Chemical Co., Ltd. ・ Hydroquinone: hydroquinone, manufactured by Seiko Chemical Co., Ltd. ・ Phenothiazine: phenothiazine, manufactured by Seiko Chemical Co., Ltd. ・ Adeka Stub LA-52: Bis (1,2,2,6,6- Pentamethylpiperidin-4-yl) = 3,4-bis {[(1,2,2,6,6-pentamethylpiperidin-4-yl) oxy] carbonyl} hexane geoate, ADEKA, ADK STAB LA- 82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, ADEKA・ Adekastab LA-7RD: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, manufactured by ADEKA ・ Adekastab LA-81: Carbonic acid = bis (2,2,6,6-tetramethyl- 1-undecyloxypiperidin-4-yl), manufactured by ADEKA, Tinuvin 123: bis [2,2,6,6-tetramethyl-1- (octyloxy) piperidin-4-yl] decanedioate, BASF・ Ozonon 35: N-1-methylheptyl-N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd. α-tocopherol: Vitamin E, 2,5,7,8-tetramethyl-2- (4 8,12-trimethyltridecan-1-yl) chroman-6-ol, manufactured by Tokyo Chemical Industry Co., Ltd.
In the active energy ray-curable offset ink composition described in the examples, 4-hydroxy-2, which is a hindered amine polymerization inhibitor having a structure of an N-oxyl radical having the formula (1) as a constituent, is used as a polymerization inhibitor. By blending 2,6,6-tetramethylpiperidine-N-oxyl in the above weight% range, the gelation of the ink, which is a necessary characteristic of the present invention, does not occur even after 4 weeks, and heat of polymerization is generated. The temperature was as high as 200 ° C. or higher, and it was confirmed that the storage stability was excellent. In addition, good ink curability was obtained.
比較例に述べる活性エネルギー線硬化型オフセットインキ組成物では、重合禁止剤を配合しない、あるいは前記（１）式に示す化学構造を持たない重合禁止剤を配合した組成物においては、４週間経過時点でゲル化が発生してしまい、重合熱発生温度も低く、また前記（１）式を構成要件とするＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤である４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルを使用した場合であっても前記の重量％の範囲を超えて多量配合した場合は、インキ硬化性が不良となることを確認した。
In the active energy ray-curable offset ink composition described in the comparative example, a polymerization inhibitor is not blended, or a composition blended with a polymerization inhibitor that does not have the chemical structure represented by the above formula (1) has passed four weeks. 4-Hydroxy-2,2, which is a hindered amine polymerization inhibitor having a structure of N-oxyl radical having the above formula (1) as a constituent element. Even when 6,6-tetramethylpiperidine-N-oxyl was used, it was confirmed that if it was added in a large amount exceeding the above-mentioned range by weight, the ink curability was poor.
本発明の活性エネルギー線硬化型オフセットインキ組成物およびそれを用いた印刷物は、安全性、衛生性を重んじる玩具、各種食品包材に加え、サニタリー・コスメ・医薬品等の包装、充填用途に幅広く展開され得る。
The active energy ray-curable offset ink composition of the present invention and printed materials using the same are widely used for sanitary, cosmetics and pharmaceutical packaging and filling applications, in addition to toys and food packaging materials that emphasize safety and hygiene. Can be done.
Claims (3)
- 顔料、重合性モノマー、及び重合禁止剤組成部を含有する活性エネルギー線硬化型オフセットインキ組成物であって、前記重合禁止剤組成物として一般式（１）式で示されるＮ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤を活性エネルギー線硬化型オフセットインキ組成物中に０．０１～０．８重量％有し、且つ一般式（１）中のＺが水酸基、Ｏ－メタクロイル基、置換基を有してもよいビニル基、炭素数１～１２のアルキル基、炭素数１～１２のシクロアルキル基、ハロゲン原子、アセタミド基、又はアセタミジル基であることを特徴とする活性エネルギー線硬化型オフセットインキ組成物。
- 前記Ｎ－オキシルラジカルの構造を有するヒンダードアミン系重合禁止剤が、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルである活性エネルギー線硬化型オフセットインキ組成物。 An active energy ray-curable offset ink composition, wherein the hindered amine polymerization inhibitor having an N-oxyl radical structure is 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
- 請求項１又は２の何れか１つに記載の活性エネルギー線硬化型オフセットインキ組成物を用いたオフセット印刷物。 The offset printed matter using the active energy ray hardening-type offset ink composition as described in any one of Claim 1 or 2.
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| JP2013-160412 | 2013-08-01 | ||
| JP2013160412 | 2013-08-01 |
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