JP2016155965A - Aqueous printing ink composition for paper container - Google Patents
Aqueous printing ink composition for paper container Download PDFInfo
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- JP2016155965A JP2016155965A JP2015036090A JP2015036090A JP2016155965A JP 2016155965 A JP2016155965 A JP 2016155965A JP 2015036090 A JP2015036090 A JP 2015036090A JP 2015036090 A JP2015036090 A JP 2015036090A JP 2016155965 A JP2016155965 A JP 2016155965A
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- meth
- ink composition
- acrylic
- water
- weight
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- Granted
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- 238000007639 printing Methods 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000839 emulsion Substances 0.000 claims abstract description 48
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000049 pigment Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 229960002887 deanol Drugs 0.000 claims description 6
- 239000012972 dimethylethanolamine Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000976 ink Substances 0.000 description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 10
- -1 ethylhexyl Chemical group 0.000 description 10
- 229940097275 indigo Drugs 0.000 description 10
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920005692 JONCRYL® Polymers 0.000 description 2
- 229920005732 JONCRYL® 678 Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 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 2
- 238000007865 diluting Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 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
- 230000007704 transition Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は紙器用水性印刷インキ組成物に関する。より詳しくは、各種印刷用紙にグラビア印刷を行った際に、良好な印刷効果を有し、優れた品質の印刷物を得るのに適した紙器用水性印刷インキ組成物に関する。 The present invention relates to a water-based printing ink composition for paper containers. More specifically, the present invention relates to a water-based printing ink composition for paper containers that has a good printing effect and is suitable for obtaining an excellent quality printed matter when gravure printing is performed on various printing papers.
有機溶剤による大気汚染等の環境問題、作業環境の安全衛生問題、防災といった観点から、印刷インキや塗料の分野では古くから脱有機溶剤化・水性化が検討されてきた。 From the viewpoint of environmental problems such as air pollution caused by organic solvents, safety and health problems in the work environment, and disaster prevention, removal of organic solvents and water-based solutions have long been studied in the field of printing inks and paints.
また、実用化されている水性グラビアインキのバインダー成分は、コア/シェル型のアクリルエマルションやアルカリ可溶性アクリル樹脂を1種類または2種類を混合して使用している場合が殆どである。 In addition, the binder component of water-based gravure ink that has been put into practical use is mostly a case where a core / shell type acrylic emulsion or an alkali-soluble acrylic resin is used alone or in combination.
さらに、前記コア/シェル型のアクリルエマルションまたはアルカリ可溶性アクリル樹脂をメインバインダーとして使用した場合、コア/シェル型のアクリルエマルションの含有量が高くなるほど、光沢に優れた印刷物を与えるが、アルコール溶解性に乏しくアルコール希釈性が不安定となり、アルカリ可溶性アクリル樹脂の含有量が高くなると、印刷インキを重ね印刷したときに、先に印刷したインキ被膜上へ後から印刷した印刷インキが良好な転移性を示さず、色調再現性が劣る現象（汚れ、ユズ肌、逆トラッピング等）が発生し、美粧性に難点が発生することがあった。 Furthermore, when the core / shell type acrylic emulsion or alkali-soluble acrylic resin is used as the main binder, the higher the content of the core / shell type acrylic emulsion, the more excellent the glossy printed matter. If the alcohol dilution becomes unstable and the content of alkali-soluble acrylic resin becomes high, when printing ink is overprinted, the printing ink printed on the previously printed ink film shows good transferability. In other words, a phenomenon in which the color tone reproducibility is inferior (dirt, dirty skin, reverse trapping, etc.) occurs, which may cause problems in cosmetics.
本発明の目的は、コア/シェル型のアクリルエマルションとアルカリ可溶性アクリル樹脂の混合系紙器用水性印刷インキ組成物において、アルコール希釈性を維持しつつ重ね印刷のインキ転移性が良好であり、印刷物の光沢に優れる印刷インキ組成物を提供することにある。 The object of the present invention is to provide a water-based printing ink composition for a paper container mixed with a core / shell type acrylic emulsion and an alkali-soluble acrylic resin. The object is to provide a printing ink composition having excellent gloss.
すなわち、本発明は、顔料と、水性バインダー樹脂と、水に可溶な有機溶媒と、水とを含有する紙器用水性印刷インキ組成物であって、前記水性バインダー樹脂がアクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）を含み下記の１）、２）であることを特徴とする紙器用水性印刷インキ組成物に関する。
１）アクリルエマルジョン（Ａ）がコア／シェル構造を有し、ガラス転移温度が５０℃以下であり、シェル部分が（メタ）アクリル酸エステル２０〜６０重量％、（メタ）アクリル酸２〜１０重量％、コア部分がスチレン１５〜４０重量％、（メタ）アクリル酸エステル１０〜３０重量％である。但し、シェル部分とコア部分をあわせて１００重量％とする
２）前記アクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）の固形分の重量比率が９５：５〜８０：２０である。
That is, the present invention is an aqueous printing ink composition for paper containers containing a pigment, an aqueous binder resin, an organic solvent soluble in water, and water, wherein the aqueous binder resin is an acrylic emulsion (A) and It is related with the water-based printing ink composition for paper containers characterized by being following 1) and 2) including an alkali-soluble acrylic resin (B).
1) Acrylic emulsion (A) has a core / shell structure, a glass transition temperature of 50 ° C. or lower, and a shell portion of 20 to 60% by weight of (meth) acrylic acid ester, 2 to 10% by weight of (meth) acrylic acid. %, The core part is 15 to 40% by weight of styrene, and 10 to 30% by weight of (meth) acrylic acid ester. However, the shell portion and the core portion are combined to be 100% by weight. 2) The weight ratio of the solid content of the acrylic emulsion (A) and the alkali-soluble acrylic resin (B) is 95: 5 to 80:20.
また、本発明はアクリルエマルジョン（Ａ）のコア／シェル比が３０：７０〜６０：４０であり、アクリルエマルジョン（Ａ）がジメチルエタノールアミンで中和されていることを特徴とする紙器用水性印刷インキ組成物関する。 In the present invention, the core / shell ratio of the acrylic emulsion (A) is 30:70 to 60:40, and the acrylic emulsion (A) is neutralized with dimethylethanolamine. It relates to an ink composition.
加えて、印刷紙基材に前記印刷インキ組成物を印刷した印刷物に関する。 In addition, the present invention relates to a printed material obtained by printing the printing ink composition on a printing paper substrate.
発明の紙器用水性印刷インキ組成物は、ガラス転移温度が５０℃以下のアクリルエマルションとアルカリ可溶性アクリル樹脂をインキバインダーとして用いることにより、重ね印刷のインキ転移性が良好で色調再現性が向上した印刷物を提供することができる。 The water-based printing ink composition for paper containers of the invention is a printed matter having good ink transferability and improved color tone reproducibility of overprinting by using an acrylic emulsion having a glass transition temperature of 50 ° C. or less and an alkali-soluble acrylic resin as an ink binder. Can be provided.
本発明の水性印刷インキ組成物は、顔料、水性バインダー樹脂が下記１）、２）である事を特徴とするアクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）、水に可溶な有機溶媒、水、各種添加剤等を配合し、公知の分散機、混合機、混練機等により分散、混合、混練することにより製造される。
１）アクリルエマルジョン（Ａ）がコア／シェル構造を有し、ガラス転移温度が５０℃以下であり、シェル部分が（メタ）アクリル酸エステル２０〜６０重量％、（メタ）アクリル酸２〜１０重量％、コア部分がスチレン１５〜４０重量％、（メタ）アクリル酸エステル１０〜３０重量％である。但し、シェル部分とコア部分をあわせて１００重量％とする
２）前記アクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）の固形分の重量比率が９５：５〜８０：２０である。
The aqueous printing ink composition of the present invention comprises an acrylic emulsion (A), an alkali-soluble acrylic resin (B), and a water-soluble organic solvent, wherein the pigment and aqueous binder resin are the following 1) and 2): , Water, various additives, and the like, and are manufactured by dispersing, mixing, and kneading using a known disperser, mixer, kneader, or the like.
1) Acrylic emulsion (A) has a core / shell structure, a glass transition temperature of 50 ° C. or lower, and a shell portion of 20 to 60% by weight of (meth) acrylic acid ester, 2 to 10% by weight of (meth) acrylic acid. %, The core part is 15 to 40% by weight of styrene, and 10 to 30% by weight of (meth) acrylic acid ester. However, the shell portion and the core portion are combined to be 100% by weight. 2) The weight ratio of the solid content of the acrylic emulsion (A) and the alkali-soluble acrylic resin (B) is 95: 5 to 80:20.
本発明で用いられるアクリルエマルジョン（Ａ）のガラス転移温度は５０℃以下であることが必要であり、５０℃より高いと造膜性が低くなり、印刷インキを重ね印刷したときに、先に印刷したインキ被膜上へ後から印刷した印刷インキが良好な転移性を示さず、色調再現性が劣る。 The glass transition temperature of the acrylic emulsion (A) used in the present invention needs to be 50 ° C. or lower. If it is higher than 50 ° C., the film-forming property is lowered, and when the printing ink is overprinted, it is printed first. The printing ink printed on the ink coating afterwards does not show good transferability and color tone reproducibility is poor.
本発明で言うアクリルエマルジョン（Ａ）のガラス転移温度（Ｔｇ）は、各単量体から形成され得る各ホモポリマーＴｇ、各単量体の重量分率から、ＦＯＸの式に基づいた計算によるガラス転移点であり、コア部分とシェル部分を合わせた一緒に計算したものである。
１／Ｔｇ＝Σ（Ｗｎ／Ｔｇｎ）
Ｔｇ ：共重合体の計算Ｔｇ（絶対温度）
Ｗｎ ：単量体ｎの重量分率（％）
Ｔｇｎ：単量体ｎのホモポリマーのガラス転移温度（絶対温度）
The glass transition temperature (Tg) of the acrylic emulsion (A) referred to in the present invention is determined by calculating the glass based on the formula of FOX from each homopolymer Tg that can be formed from each monomer and the weight fraction of each monomer. This is the transition point, calculated together with the core and shell parts.
1 / Tg = Σ (Wn / Tgn)
Tg: Calculation of copolymer Tg (absolute temperature)
Wn: weight fraction (%) of monomer n
Tgn: glass transition temperature (absolute temperature) of homopolymer of monomer n
本発明のアクリルエマルション（Ａ）のシェル部分を形成し得る（メタ）アクリル酸エステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル鎖を有する（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレートト等の水酸基を有する（メタ）アクリレート。シクロヘキシル（メタ）アクリレート等の脂環構造を有する（メタ）アクリレートが挙げられ、これら１種または２種以上の組み合わせて用いる事ができる。（メタ）アクリル酸エステルの使用量はアクリルエマルジョン（Ａ）総量の内、２０〜６０重量％であることが必要である。２０重量％よりも少ないと印刷物の光沢が低下し、６０重量％よりも多いと造膜不良を起こし、印刷物としての耐摩擦性が劣化する。 Examples of the (meth) acrylic acid ester that can form the shell portion of the acrylic emulsion (A) of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2- (Meth) acrylates having a hydroxyl group such as (meth) acrylates having an alkyl chain such as ethylhexyl (meth) acrylate and stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. Examples include (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate, and these can be used alone or in combination of two or more. The amount of the (meth) acrylic acid ester used needs to be 20 to 60% by weight in the total amount of the acrylic emulsion (A). When the amount is less than 20% by weight, the gloss of the printed matter is lowered. When the amount is more than 60% by weight, film formation is poor, and the friction resistance as the printed matter is deteriorated.
本発明のアクリルエマルション（Ａ）のシェル部分を形成し得る（メタ）アクリル酸としては、アクリル酸、メタアクリル酸がある。（メタ）アクリル酸の使用量はアクリルエマルジョン（Ａ）総量の内、２〜１０重量％であることが必要である。２重量％よりも少なくても、また１０重量％より多くても、印刷物の光沢が低下する。 Examples of (meth) acrylic acid that can form the shell portion of the acrylic emulsion (A) of the present invention include acrylic acid and methacrylic acid. The amount of (meth) acrylic acid used needs to be 2 to 10% by weight in the total amount of the acrylic emulsion (A). If it is less than 2% by weight or more than 10% by weight, the gloss of the printed matter is lowered.
本発明のアクリルエマルション（Ａ）のコア部分を形成し得るスチレンは、スチレン、α−メチルスチレンが挙げられ、これら1種または２種の組み合わせて用いる事ができる。スチレンは１５〜４０重量％使用することが必要である。１５重量％より少ないと印刷物の光沢が低下し、４０重量％より多いと溶解性が劣化する為、インキの貯蔵安定性に問題が生じやすい。 Examples of styrene that can form the core portion of the acrylic emulsion (A) of the present invention include styrene and α-methylstyrene, and these can be used alone or in combination. It is necessary to use 15 to 40% by weight of styrene. If the amount is less than 15% by weight, the gloss of the printed matter is lowered. If the amount is more than 40% by weight, the solubility is deteriorated, so that a problem is likely to occur in the storage stability of the ink.
本発明のアクリルエマルション（Ａ）のコア部分を形成し得る（メタ）アクリル酸エステルとしては、前記したメチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル鎖を有する（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレートト等の水酸基を有する（メタ）アクリレート。シクロヘキシル（メタ）アクリレート等の脂環構造を有する（メタ）アクリレートが挙げられ、これら１種または２種以上の組み合わせて用いる事ができる。（メタ）アクリル酸エステルの使用量はアクリルエマルジョン（Ａ）総量の内、１０〜３０重量％であることが必要である。１０重量％よりも少ないと印刷物の光沢が低下し、３０重量％よりも多いと造膜不良を起こし、印刷物としての耐摩擦性が劣化する。
コア部分の（メタ）アクリル酸エステルと、シェル部分の（メタ）アクリル酸エステルは、同じであっても、異なっていてもよい。また、コア部分、シェル部分は、（メタ）アクリル酸エステル、（メタ）アクリル酸、スチレン以外のこれらと重合可能な成分と一緒に重合されていてもよい。
Examples of the (meth) acrylic acid ester that can form the core part of the acrylic emulsion (A) of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) having a hydroxyl group such as (meth) acrylate having an alkyl chain such as 2-ethylhexyl (meth) acrylate and stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate Acrylate. Examples include (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate, and these can be used alone or in combination of two or more. The amount of the (meth) acrylic acid ester used needs to be 10 to 30% by weight in the total amount of the acrylic emulsion (A). When the amount is less than 10% by weight, the gloss of the printed matter is lowered.
The (meth) acrylic acid ester in the core part and the (meth) acrylic acid ester in the shell part may be the same or different. Moreover, the core part and the shell part may be polymerized together with components polymerizable with these other than (meth) acrylic acid ester, (meth) acrylic acid and styrene.
本発明の水性印刷インキ組成物におけるアクリルエマルジョン（Ａ）は、上記（メタ）アクリル酸エステル、（メタ）アクリル酸とを共重合して得られた高分子乳化剤の存在下において、共重合可能なスチレン及び(メタ)アクリル酸エステルを乳化重合して得られるコア／シェル構造を有するアクリルエマルジョンである。 The acrylic emulsion (A) in the aqueous printing ink composition of the present invention can be copolymerized in the presence of a polymer emulsifier obtained by copolymerizing the above (meth) acrylic acid ester and (meth) acrylic acid. It is an acrylic emulsion having a core / shell structure obtained by emulsion polymerization of styrene and (meth) acrylic acid ester.
本発明のアクリルエマルション（Ａ）のコア/シェル比率（コア部分とシェル部分との重量比）は３０：７０〜６０：４０であることが好ましい。コア比率が３０より小さくなると、皮膜物性が低下しやすい傾向であり、コア比率が６０より大きくなるとアクリルエマルション（Ａ）の安定性の劣る傾向であり、インキの貯蔵安定性に問題が生じやすい。 The core / shell ratio (weight ratio of the core portion to the shell portion) of the acrylic emulsion (A) of the present invention is preferably 30:70 to 60:40. When the core ratio is less than 30, the physical properties of the film tend to be lowered. When the core ratio is greater than 60, the stability of the acrylic emulsion (A) tends to be inferior, and a problem is likely to occur in the storage stability of the ink.
アクリルエマルション（Ａ）の合成に用いられる中和剤としてはアンモニア、有機アミン、アルカリ金属水酸化物等を使用できる。有機アミンとしてはジエチルアミン、トリエチルアミン、モノエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン等が挙げられる。アルカリ金属の水酸化物としては水酸化ナトリウム、水酸化カリウム等がある。好ましくは有機アミンであり、更に好ましくはジメチルエタノールアミンである。ジエタノールアミンを用いると再溶解性の点で好ましく、良好な網点再現性が得られる。 As the neutralizing agent used for the synthesis of the acrylic emulsion (A), ammonia, an organic amine, an alkali metal hydroxide, or the like can be used. Examples of the organic amine include diethylamine, triethylamine, monoethanolamine, dimethylethanolamine, diethylethanolamine and the like. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. An organic amine is preferable, and dimethylethanolamine is more preferable. Use of diethanolamine is preferable from the viewpoint of re-solubility, and good halftone dot reproducibility can be obtained.
重合反応には、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩またはアゾビス系カチオン塩もしくは水酸基付加物等の水溶性の熱分解型重合開始剤を用いることができる。
またレドックス開始剤を用いることもできる。レドックス開始剤としては、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイドなどの有機過酸化物とロンガリット、メタ重亜硫酸ナトリウムなどの還元剤との組み合わせ、または過硫酸カリウム、過硫酸アンモニウムとロンガリット、チオ硫酸ナトリウムなどとの組み合わせ、過酸化水素水とアスコルビン酸との組み合わせ等が用いられる。
For the polymerization reaction, a persulfate such as potassium persulfate or ammonium persulfate, or a water-soluble pyrolytic polymerization initiator such as an azobis cation salt or a hydroxyl group adduct can be used.
A redox initiator can also be used. Redox initiators include combinations of organic peroxides such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and reducing agents such as Rongalite, sodium metabisulfite, or potassium persulfate, ammonium persulfate and A combination with Rongalite, sodium thiosulfate, or the like, or a combination of hydrogen peroxide and ascorbic acid is used.
本発明に用いられるアルカリ可溶性アクリル樹脂は（Ｂ）、外観が透明〜ほぼ透明であり、中和剤は前記したアンモニア、有機アミン、アルカリ金属水酸化物等を使用したものであれば、特に限定されるものではなく、市販品を用いてもよい。例えば、ＢＡＳＦ社製「Ｊｏｎｃｒｙｌ ６７、Ｊｏｎｃｒｙｌ ６７８、Ｊｏｎｃｒｙｌ ６８０、Ｊｏｎｃｒｙｌ ８１９」などがある。 The alkali-soluble acrylic resin used in the present invention is particularly limited as long as the appearance is transparent to almost transparent and the neutralizing agent uses ammonia, organic amine, alkali metal hydroxide, or the like. A commercially available product may be used instead. For example, “Joncry 67, Joncryl 678, Joncryl 680, Joncryl 819” manufactured by BASF may be used.
本発明の水性印刷インキ組成物において、アクリルエマルション（Ａ）とアルカリ可溶性アクリル樹脂は（Ｂ）の固形分の重量比率は９５：５〜８０：２０の範囲である必要があり、より好ましくは９３：７〜８５：１５である。アクリルエマルション（Ａ）の固形分の重量比率が９５を超える範囲では、アルコール希釈性に劣り、インキの貯蔵安定性に問題が生じやすく、固形分の重量比率が８０未満の範囲では、網点再現性が劣る傾向となる。 In the water-based printing ink composition of the present invention, the weight ratio of the solid content of the acrylic emulsion (A) and the alkali-soluble acrylic resin needs to be in the range of 95: 5 to 80:20, more preferably 93. : 7 to 85:15. When the weight ratio of the solid content of the acrylic emulsion (A) exceeds 95, the alcohol dilution is inferior and the storage stability of the ink is liable to occur. When the weight ratio of the solid content is less than 80, halftone dot reproduction is achieved. Tend to be inferior.
本発明の紙器用水性印刷インキ組成物は、顔料、水性バインダー樹脂、水に可溶な有機溶媒、および水からなる。各種印刷紙基材にグラビア印刷した際に、良好な光沢、乾燥性を得る為には、印刷インキ組成物中に水性バインダー樹脂を固形分として組成物全体の５〜５０重量％含有することが重要であり、５重量％より少ない場合、充分な光沢、乾燥性を得ることができず、また５０重量％より多い場合、充分な流動性、レベリング性が得られにくく好ましくない。 The aqueous printing ink composition for paper containers of the present invention comprises a pigment, an aqueous binder resin, an organic solvent soluble in water, and water. In order to obtain good gloss and drying properties when gravure printing is performed on various printing paper substrates, the printing ink composition may contain 5 to 50% by weight of the entire composition as a solid content of an aqueous binder resin. It is important, and if it is less than 5% by weight, sufficient gloss and drying properties cannot be obtained, and if it is more than 50% by weight, it is difficult to obtain sufficient fluidity and leveling properties.
本発明に用いる顔料には、一般のインキ、塗料、および記録剤などに使用されている有機、無機顔料や染料を挙げることができる。有機顔料としてはアゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などの顔料が挙げられる。藍インキには銅フタロシアニン、透明黄インキにはコスト・耐光性の点からC．I．Pigment ＮＯ yellow83を用いることが好ましい。
無機顔料としては、カーボンブラック、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、ベンガラ、アルミニウム、カオリンクレー、タルク、マイカ（雲母）などが挙げられる。白インキには酸化チタン、墨インキにはカーボンブラック、金、銀インキにはアルミニウム、パールインキにはマイカ（雲母）を使用することがコストや着色力の点から好ましい。
Examples of the pigment used in the present invention include organic and inorganic pigments and dyes used in general inks, paints, and recording agents. Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline pigments Is mentioned. Indigo ink contains copper phthalocyanine, and transparent yellow ink uses C.I. I. Pigment NO yellow 83 is preferably used.
Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, kaolin clay, talc, mica (mica) and the like. From the viewpoints of cost and coloring power, it is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for silver ink, and mica for pearl ink.
顔料はインキの濃度・着色力を確保するのに充分な量、すなわちインキの総重量に対して1〜５０重量％の割合で含まれることが好ましい。また、着色剤は単独で、または2種類以上を併用して用いることが出来、着色剤を含まなくとも、同等の重ね刷り適性が得られる。 The pigment is preferably contained in an amount sufficient to ensure the concentration and coloring power of the ink, that is, in a proportion of 1 to 50% by weight based on the total weight of the ink. In addition, the colorant can be used alone or in combination of two or more, and even if it does not contain a colorant, the same overprintability can be obtained.
水に可溶な有機溶媒としては、メチルアルコール、エチルアルコール、イソプロピルアルコール、Ｎ−プロピルアルコール等のアルコール類、エチレングリコール、プロピレングリコール等のグリコール類、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル等のグリコールエーテル類が挙げられる。水と水に可溶な有機溶媒の重量比率は、インキの貯蔵安定性と乾燥の観点から、水とアルコール類の重量比率は、９０：１０〜６０：４０であることが好ましい。 Examples of water-soluble organic solvents include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and N-propyl alcohol, glycols such as ethylene glycol and propylene glycol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Examples include glycol ethers such as monoethyl ether and diethylene glycol monobutyl ether. From the viewpoint of storage stability of ink and drying, the weight ratio of water to water-soluble organic solvent is preferably 90:10 to 60:40.
本発明の水性印刷インキ組成物の製造は、公知の方法で行なうことができる。例えば、顔料をアクリルエマルジョン（Ａ）、水、水に可溶な有機溶媒、必要に応じてその他の併用樹脂、分散剤等により分散させた顔料分散体を製造し、得られた顔料分散体に、アクリルエマルジョン（Ａ）、アルカリ可溶性アクリル樹脂（Ｂ）、必要に応じてその他の併用樹脂、添加剤などからなる調整液を混合する方法で得られる。 The water-based printing ink composition of the present invention can be produced by a known method. For example, a pigment dispersion in which a pigment is dispersed with an acrylic emulsion (A), water, an organic solvent soluble in water, and if necessary, other combined resin, a dispersant, etc. is manufactured, and the resulting pigment dispersion , An acrylic emulsion (A), an alkali-soluble acrylic resin (B), and, if necessary, another adjustment resin, an adjustment liquid composed of additives, and the like are obtained by a method of mixing.
本発明の水性印刷インキ組成物には、上記構成材料の他に、必要に応じて、気相法シリカ、湿式法シリカ、有機処理シリカ、アルミナ処理シリカ等の微粉末シリカ、ポリエチレンワックス、消泡剤、レベリング剤、粘着性付与剤、防腐剤、抗菌剤、防錆剤等の添加剤も配合することができる。 In the aqueous printing ink composition of the present invention, in addition to the above-mentioned constituent materials, if necessary, fine-powder silica such as vapor-phase method silica, wet method silica, organic treatment silica, alumina treatment silica, polyethylene wax, antifoaming Additives such as additives, leveling agents, tackifiers, antiseptics, antibacterial agents, and rust inhibitors can also be blended.
以上の材料と製造方法から得られた印刷インキ組成物は、印刷時に、必要に応じて水、水に可溶な有機溶媒からなる希釈溶剤で、適宜希釈しグラビア印刷方式で、各種紙基材に印刷することができる。例えば、アート紙、コート紙、上質紙等がある。また、利用可能な希釈溶剤は水とアルコール系との混合溶剤が好ましく、重量比率は、インキの貯蔵安定性と乾燥の観点から、好ましくは、５０：５０〜９０：１０が望ましい。
さらに、グラビア印刷機によって印刷され得られた印刷物は、様々な用途に応じて後加工され、食品など商品の包装、とりわけ紙器用に好適に使用される。
The printing ink composition obtained from the above-described materials and production method is appropriately diluted with a diluting solvent composed of water or a water-soluble organic solvent as necessary at the time of printing. Can be printed on. For example, there are art paper, coated paper, high-quality paper, and the like. The dilutable solvent that can be used is preferably a mixed solvent of water and alcohol, and the weight ratio is preferably 50:50 to 90:10 from the viewpoint of storage stability of ink and drying.
Furthermore, the printed matter obtained by printing with a gravure printing machine is post-processed according to various uses, and is suitably used for packaging of products such as food, especially for paper containers.
[実施例]
以下，実施例および比較例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、各実施例中の「部」および「％」は「重量部」および「重量％」を表す。
[Example]
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”.
＜アクリルエマルジョン（Ａ）の合成＞
先ず、実施例、比較例に使用するコア／シェル型のアクリルエマルジョン（Ａ）を合成した。合成例中の「部」は上記と同様である。
（合成例１）
窒素ガス置換した四つ口フラスコに、イソプロピルアルコールを１００部仕込み、温度を８０〜８２℃に上げた後、滴下ロートに仕込んだアクリル酸５部、ブチルアクリレート１５部、メチルメタクリレート４０部、過酸化ベンゾイル２．５部の混合物を２時間かけて滴下した。滴下終了後、過酸化ベンゾイル０．５部を追加し、更に２時間反応させた。温度を４０℃に下げ、ジメチルエタノールアミン、イオン交換水を添加した。その後、反応フラスコの温度を８０〜８２℃に上げ、ストリッピングを行ない、最終的に固形分３０％の水溶性樹脂を得た。
上記で得た水溶性樹脂全量、イオン交換水１０部を反応フラスコに仕込み、温度を８０℃〜８２℃に上げた後、過硫酸カリウムを０．８部添加し、スチレン２０部、２−エチルヘキシルアクリレート２０部の混合物を２時間かけて滴下した。滴下終了後、過硫酸カリウム０．２部を添加し、２時間反応させた。このようにして得られたアクリルエマルジョン（樹脂（Ａ１））の固形分は４０％であった。
<Synthesis of acrylic emulsion (A)>
First, a core / shell type acrylic emulsion (A) used in Examples and Comparative Examples was synthesized. The “part” in the synthesis example is the same as described above.
(Synthesis Example 1)
In a four-necked flask purged with nitrogen gas, 100 parts of isopropyl alcohol was added, the temperature was raised to 80-82 ° C., and 5 parts of acrylic acid, 15 parts of butyl acrylate, 40 parts of methyl methacrylate, and peroxide were added to the dropping funnel. A mixture of 2.5 parts of benzoyl was added dropwise over 2 hours. After completion of the dropwise addition, 0.5 part of benzoyl peroxide was added, and the mixture was further reacted for 2 hours. The temperature was lowered to 40 ° C., and dimethylethanolamine and ion exchange water were added. Thereafter, the temperature of the reaction flask was raised to 80 to 82 ° C., and stripping was performed to finally obtain a water-soluble resin having a solid content of 30%.
The total amount of the water-soluble resin obtained above and 10 parts of ion exchange water were charged into a reaction flask, the temperature was raised to 80 ° C. to 82 ° C., 0.8 part of potassium persulfate was added, 20 parts of styrene, and 2-ethylhexyl. A mixture of 20 parts of acrylate was added dropwise over 2 hours. After completion of dropping, 0.2 part of potassium persulfate was added and reacted for 2 hours. The acrylic emulsion (resin (A1)) thus obtained had a solid content of 40%.
（合成例２〜１９）
合成例２〜１９に付いては合成例１と同様な方法で重合を行い、アクリルエマルジョンである樹脂（Ａ２）〜樹脂（Ａ１９）を得た。それらのモノマーの配合を表１に示す。
尚、いずれの合成例においても、シェル部分を構成する水溶性樹脂は固形分が３０％になるよう調整し、その全量を使用した。また、最終的なアクリルエマルジョンの固形分が４０％になるように調整した。
また、シェル部分の合成における中和剤は、合成例１〜１０、１２〜１９においてはジメチルエタノールアミン、合成例１１においてはアンモニア水を使用し、ストリッピングによる留去も考慮し、カルボキシル基に対して最終的には１１０％中和とした。
(Synthesis Examples 2 to 19)
About the synthesis examples 2-19, it superposed | polymerized by the method similar to the synthesis example 1, and resin (A2)-resin (A19) which are acrylic emulsions were obtained. Table 1 shows the composition of these monomers.
In any of the synthesis examples, the water-soluble resin constituting the shell portion was adjusted so that the solid content was 30%, and the total amount was used. The final acrylic emulsion was adjusted so that the solid content was 40%.
Further, as a neutralizing agent in the synthesis of the shell portion, dimethylethanolamine is used in Synthesis Examples 1 to 10 and 12 to 19, and ammonia water is used in Synthesis Example 11, and in consideration of distillation by stripping, In contrast, the final neutralization was 110%.
＜アルカリ可溶性アクリル樹脂（Ｂ）の調整＞
アルカリ可溶性アクリル樹脂（Ｊｏｎｃｒｙｌ ６７８ ＢＡＳＦ社製）２０部、２５％アンモニア水溶液５部、水７５部を混合溶解させて、固形分２０％の試験用アクリルワニス（ワニス（Ｂ））を得た。
[実施例１]
<Preparation of alkali-soluble acrylic resin (B)>
20 parts of alkali-soluble acrylic resin (manufactured by Joncryl 678 BASF), 5 parts of 25% aqueous ammonia solution and 75 parts of water were mixed and dissolved to obtain a test acrylic varnish (varnish (B)) having a solid content of 20%.
[Example 1]
次に、黄顔料（山陽色素（株）社製「ピグメントイエロー１４５０」）：１０部、合成例１で得られたアクリルエマルジョン（樹脂（Ａ１））２０部（固形４０％）、水１０部、イソプロピルアルコール１０部をペイントコンディショナーにて６０分間分散した顔料分散体に対し、上記アクリルエマルジョン２０部（固形４０%）、試験用アクリルワニス（ワニス（Ｂ））１０部、ポリエチレンワックス ２．５部、シリコーン系消泡剤０．０１部、 水 １０部、イソプロピルアルコール７．４９部を調整液として添加し、更にペイントコンディショナーにて１０分間分散して、下地用黄インキ組成物を調製した。
また、重ね刷り用として、藍インキ組成物を以下に示す通りに調製した。
藍顔料（ＤＩＣ（株）社製「ファストゲンブルーＦＧＦ−ＳＤ」）：１０部、合成例１で得られたアクリルエマルジョン（樹脂（Ａ１））２０部（固形４０％）、水１０部、イソプロピルアルコール１０部をペイントコンディショナーにて６０分間分散した顔料分散体に対し、上記アクリルエマルジョン２０部（固形４０%）、試験用アクリルワニス（ワニス（Ｂ））１０部、ポリエチレンワックス ２．５部、シリコーン系消泡剤０．０１部、水 １０部、イソプロピルアルコール７．４９部を調整液として添加し、更にペイントコンディショナーにて１０分間分散して、重ね刷り用藍インキ組成物を調製した。
次いで、これらのインキ組成物を、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップＮｏ．３で１５秒になるように粘度を調整してインキ組成物を得た。
なお希釈溶剤として水： イソプロピルアルコール＝ ３０： ７０（重量比）を用いた。
Next, yellow pigment (“Pigment Yellow 1450” manufactured by Sanyo Color Co., Ltd.): 10 parts, acrylic emulsion (resin (A1)) obtained in Synthesis Example 1, 20 parts (solid 40%), water 10 parts, For the pigment dispersion obtained by dispersing 10 parts of isopropyl alcohol for 60 minutes with a paint conditioner, 20 parts of the acrylic emulsion (solid 40%), 10 parts of a test acrylic varnish (varnish (B)), 2.5 parts of polyethylene wax, 0.01 parts of a silicone-based antifoaming agent, 10 parts of water and 7.49 parts of isopropyl alcohol were added as adjustment liquids, and further dispersed for 10 minutes with a paint conditioner to prepare a yellow ink composition for a base.
Moreover, the indigo ink composition was prepared as shown below for overprinting.
Indigo pigment (“Fastgen Blue FGF-SD” manufactured by DIC Corporation): 10 parts, 20 parts of acrylic emulsion (resin (A1)) obtained in Synthesis Example 1 (resin (A1)) (solid 40%), 10 parts of water, isopropyl For the pigment dispersion obtained by dispersing 10 parts of alcohol in a paint conditioner for 60 minutes, 20 parts of the above acrylic emulsion (solid 40%), 10 parts of acrylic varnish for test (varnish (B)), 2.5 parts of polyethylene wax, silicone An antifoaming agent (0.01 part), water (10 parts), and isopropyl alcohol (7.49 parts) were added as adjustment liquids, and further dispersed in a paint conditioner for 10 minutes to prepare an indigo ink composition for overprinting.
Subsequently, these ink compositions were used as a viscosity adjusting solvent using a diluting solvent. 3 was adjusted to a viscosity of 15 seconds to obtain an ink composition.
In addition, water: isopropyl alcohol = 30: 70 (weight ratio) was used as a dilution solvent.
［実施例２〜１４、比較例１〜９］
実施例２〜１４および比較例１〜９の下地用黄インキ組成物については、実施例１の黄顔料を用い、表２、３に示す配合により実施例１と同様な方法で調製した。重ね刷り用藍インキも同様に、実施例１の藍顔料にて、表２、３に示す配合により実施例１と同様な方法で調製した。
[Examples 2-14, Comparative Examples 1-9]
About the yellow ink composition for base | substrates of Examples 2-14 and Comparative Examples 1-9, it prepared by the method similar to Example 1 by the mixing | blending shown in Table 2, 3 using the yellow pigment of Example 1. FIG. Similarly, indigo ink for overprinting was prepared in the same manner as in Example 1 using the indigo pigment of Example 1 and the formulation shown in Tables 2 and 3.
［評価項目］
実施例１〜１４および比較例１〜９で得られた下地用黄インキ組成物及び重ね刷り用藍インキ組成物を用い、印刷用紙としてコート紙（ＣＲＣ２３０ｇ、レンゴー株式会社製）に対し、イワセ印刷機械(株)のベビー印刷機にて、黄インキ組成物は、コンベンショナル３０μベタ版にて、藍インキ組成物は、１７５ 線／ インチヘリオ彫刻製版にて重ね刷りを行い印刷物を得た。
以下に評価方法と評価基準を示す。また、評価結果を表２、３に示す。
[Evaluation item]
Using the yellow ink composition for base and the indigo ink composition for overprinting obtained in Examples 1 to 14 and Comparative Examples 1 to 9, Iwase printing was performed on coated paper (CRC 230 g, manufactured by Rengo Co., Ltd.) as printing paper. Using a baby printing machine manufactured by Kikai Co., Ltd., the yellow ink composition was overprinted with a conventional 30μ solid plate, and the indigo ink composition was overprinted with a 175 line / inch helio engraving plate to obtain a printed matter.
The evaluation method and evaluation criteria are shown below. The evaluation results are shown in Tables 2 and 3.
＜網点再現性＞
黄インキ組成物を単色刷りした印刷物、および藍インキ組成物を重ね刷りした印刷物の網点パーセントが１００％ から３％ 印刷部を、以下の評価基準で評価した。
評価基準
◎ ・・・網点パーセント１００％ 部から３％まで諧調再現性が極めて良好か つ単色刷りおよび重ね刷りでの同網点パーセントにおいて網点サイズに変 化がない。
○ ・・・網点パーセント１００％ 部から３％まで諧調再現性があり、かつ単 色刷りおよび重ね刷りでの同網点パーセントにおいて網点サイズに変化が ない。
○△ ・・・網点パーセント１００％ 部から３％まで諧調再現性があり、かつ単 色刷りおよび重ね刷りでの同網点パーセントにおいて網点サイズに少し変 化がある。
△ ・・・網点パーセント１００％ 部から１０％まで諧調再現性があり、かつ 単色刷りおよび重ね刷りでの同じ網点パーセントにおいて網点サイズに少 し変化がある。
× ・・・網点パーセント７０％ 部以下の諧調再現性がなく、かつ単色刷りお よび重ね刷りでの同じ網点パーセントにおいて網点サイズに変化がある。
なお、実用レベルは○△以上である。
<Reproducibility of halftone dots>
The dot percentage of the printed matter obtained by printing a single color of the yellow ink composition and the printed matter obtained by overprinting the indigo ink composition was 100% to 3%. The printed part was evaluated according to the following evaluation criteria.
Evaluation Criteria ◎ ・ ・ ・ Halftone dot percentage 100% From 3% to 3%, the gradation reproducibility is very good, and there is no change in halftone dot size in the same halftone dot percentage in single color printing and overprinting.
○ ... Has a tone reproduction from 100% to 3%, and there is no change in the dot size in the same dot percentage in single color printing and overprinting.
○ △ ... Halftone dot percentage is 100% to 3%, and there is a slight change in the halftone dot size at the same halftone dot percentage in single color printing and overprinting.
Δ: Halftone dot percentage 100% Tonal reproducibility from 10% to 10%, and there is a slight change in halftone dot size at the same halftone dot percentage in single color printing and overprinting.
X: Percent halftone dot: No halftone reproducibility of 70% or less, and there is a change in halftone dot size at the same halftone dot percentage in single color printing and overprinting.
Note that the practical level is ◯ Δ or more.
＜希釈インキ安定性＞
粘度調整後の黄インキ組成物及び藍インキ組成物のインキ粘度と４０℃-３０日間保管後の粘度を測定し、増粘の程度を、以下の評価基準で評価した。
粘度は離合社製のザーンカップＮｏ．３で測定した。
評価基準
◎ ・・・粘度増加なし
○ ・・・粘度増加５秒未満
△ ・・・粘度増加５〜１０秒未満
× ・・・粘度増加１０秒以上
なお、実用レベルは△以上である。
<Dilution ink stability>
The viscosity of the yellow ink composition and the indigo ink composition after viscosity adjustment and the viscosity after storage at 40 ° C. for 30 days were measured, and the degree of thickening was evaluated according to the following evaluation criteria.
The viscosity is Zahn Cup No. 3 was measured.
Evaluation Criteria ◎… No increase in viscosity ○… Increase in viscosity less than 5 seconds Δ… Increase in viscosity 5 to less than 10 seconds ×… Increase in viscosity 10 seconds or more The practical level is Δ or more.
＜光沢＞
グラデーションの１００％部の光沢値を、「ヘイズ−グロスリフレクトメーター」〔ビックケミー・ジャパン株式会社〕により６０°−６０°を測定した。
評価基準
○ ・・・光沢値４０以上
△ ・・・光沢値３０〜４０
× ・・・光沢値３０未満
なお、実用レベルは△以上である。
<Glossy>
The gloss value of 100% part of the gradation was measured at 60 ° -60 ° by “Haze-Gloss Reflectometer” [BIC Chemie Japan Co., Ltd.].
Evaluation criteria ○ ・ ・ ・ Gloss value of 40 or more △ ・ ・ ・ Gloss value of 30 to 40
X: Gloss value less than 30 The practical level is Δ or more.
表２、３からわかるとおり、実施例は、比較例に比べて良好な網点再現性、希釈インキ安定性及び光沢を示すことがわかった。さらに、実施例１は、実施例１〜１４の中で、特に網点再現性、インキ安定性及び光沢のバランスに優れていることがわかった。 As can be seen from Tables 2 and 3, it was found that the examples showed better halftone dot reproducibility, diluted ink stability and gloss than the comparative examples. Furthermore, Example 1 was found to be particularly excellent in the balance of halftone dot reproducibility, ink stability, and gloss among Examples 1-14.
Claims (4)
前記水性バインダー樹脂が、アクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）とを含み、かつ、下記の１）、２）であることを特徴とする紙用水性印刷インキ組成物。
１）アクリルエマルジョン（Ａ）が、コア／シェル構造を有し、
ガラス転移温度が５０℃以下であり、
シェル部分は、（メタ）アクリル酸エステル２０〜６０重量％、（メタ）アクリル酸２〜１０重量％が重合してなり、
コア部分は、スチレン１５〜４０重量％、（メタ）アクリル酸エステル１０〜３０重量％が重合してなる。但し、シェル部分とコア部分とをあわせて１００重量％とする
２）前記アクリルエマルジョン（Ａ）とアルカリ可溶性アクリル樹脂（Ｂ）との固形分の重量比率が９５：５〜８０：２０である。 An aqueous printing ink composition for paper containing a pigment, an aqueous binder resin, an organic solvent soluble in water, and water,
The water-based printing ink composition for paper, wherein the aqueous binder resin contains an acrylic emulsion (A) and an alkali-soluble acrylic resin (B) and is 1) or 2) below.
1) The acrylic emulsion (A) has a core / shell structure,
The glass transition temperature is 50 ° C. or less,
The shell portion is formed by polymerization of 20 to 60% by weight of (meth) acrylic acid ester and 2 to 10% by weight of (meth) acrylic acid,
The core part is formed by polymerizing 15 to 40% by weight of styrene and 10 to 30% by weight of (meth) acrylic acid ester. However, the shell portion and the core portion are combined to be 100% by weight. 2) The weight ratio of the solid content of the acrylic emulsion (A) and the alkali-soluble acrylic resin (B) is 95: 5 to 80:20.
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| JP2018158986A (en) * | 2017-03-22 | 2018-10-11 | 東洋インキＳｃホールディングス株式会社 | Aqueous flexographic ink composition for pack |
| CN109679025A (en) * | 2018-11-30 | 2019-04-26 | 广东英科集团股份有限公司 | A kind of preparation method and application of neutral emulsion |
| CN111500113A (en) * | 2020-06-05 | 2020-08-07 | 杭州海维特化工科技有限公司 | Copper plate paper gravure water-based ink and preparation method thereof |
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| JP2018158986A (en) * | 2017-03-22 | 2018-10-11 | 東洋インキＳｃホールディングス株式会社 | Aqueous flexographic ink composition for pack |
| CN109679025A (en) * | 2018-11-30 | 2019-04-26 | 广东英科集团股份有限公司 | A kind of preparation method and application of neutral emulsion |
| CN109679025B (en) * | 2018-11-30 | 2021-01-08 | 广东英科集团股份有限公司 | Preparation method and application of neutral emulsion |
| CN111500113A (en) * | 2020-06-05 | 2020-08-07 | 杭州海维特化工科技有限公司 | Copper plate paper gravure water-based ink and preparation method thereof |
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