JP5761395B2 - Gravure printing ink - Google Patents
Gravure printing ink Download PDFInfo
- Publication number
- JP5761395B2 JP5761395B2 JP2014019899A JP2014019899A JP5761395B2 JP 5761395 B2 JP5761395 B2 JP 5761395B2 JP 2014019899 A JP2014019899 A JP 2014019899A JP 2014019899 A JP2014019899 A JP 2014019899A JP 5761395 B2 JP5761395 B2 JP 5761395B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- printing
- parts
- chloride
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007646 gravure printing Methods 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920005749 polyurethane resin Polymers 0.000 claims description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000976 ink Substances 0.000 description 91
- 238000007639 printing Methods 0.000 description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 18
- -1 (hydroxyethyl) methyl Chemical group 0.000 description 14
- 239000000049 pigment Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 9
- 230000003068 static effect Effects 0.000 description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920000298 Cellophane Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
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- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000001348 alkyl chlorides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000020 Nitrocellulose Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
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- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
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- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 230000002123 temporal effect 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
- 210000003813 thumb Anatomy 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 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)
Description
本発明は、グラビア印刷インキに関し、より詳しくはグラビアインキ印刷時に発生する静電気による印刷不良を低減させることができ、さらにインキ経時安定性、印刷フィルムへの接着性、印刷物を巻き取った時のブロッキング性、ラミネート物のボイル適性などを低下させることがないグラビア印刷インキに関するものである。 The present invention relates to a gravure printing ink, and more specifically, can reduce printing defects due to static electricity generated during gravure ink printing, and further, stability over time with ink, adhesion to a printing film, blocking when a printed material is wound up. The present invention relates to a gravure printing ink that does not deteriorate the properties and the boilability of a laminate.
近年、印刷業界では生産性向上のために印刷速度が速くなっており、印刷不良が発生し易い状況になっている。印刷不良が発生し難く、印刷歩留まりが良いインキに対する要望が従来以上に求められている。 In recent years, in the printing industry, the printing speed has been increased in order to improve productivity, and printing defects are likely to occur. There is a greater demand than ever for inks that are less prone to printing defects and that have good printing yields.
一般的に、溶剤型グラビアインキでは、インキの転移時に鋭角な画像部の印刷面よりインキ飛びが発生するヒゲ(以下、ヒゲという)と、インキが霧状に飛散し印刷物を汚染するミスチング(以下、ミスチングという)といった静電気による印刷不良が、発生し易いという問題がある。 In general, in solvent-type gravure inks, whiskers (hereinafter referred to as whiskers) that cause ink splashes from the printing surface of sharp image areas during ink transfer, and misting (hereinafter referred to as ink sprays) that contaminate printed matter. Printing defects due to static electricity such as misting) are likely to occur.
ヒゲ・ミスチングは印刷速度、インキ粘度、印刷版深(インキの塗布量)、印刷室の環境(温度・湿度)、印刷機の帯電具合などの影響を受け、ヒゲ・ミスチングが発生した場合は前記のインキ粘度などの変更あるいは印刷機廻りの散水または加湿機による加湿、静電気除去テープの使用などでの物理的な徐電と印刷粘度などの印刷条件の変更でヒゲ・ミスチングの防止を行っていたが、ヒゲ・ミスチングの防止策としては充分でない状況であった。 Beard misting is affected by printing speed, ink viscosity, printing plate depth (ink application amount), printing room environment (temperature / humidity), printing machine charging condition, etc. Prevents whisker and misting by changing the ink viscosity, changing the printing conditions, such as spraying water around the printing machine, humidifying with a humidifier, and using a static elimination tape, and changing the printing viscosity. However, it was not enough to prevent beard misting.
ヒゲ・ミスチングの防止策として硝酸ヤシアルキルビス(ヒドロキシエチル)メチルとヤシアルキルビス(ヒドロキシエチル)メチルクロライドを用いる方法が特許文献1に提案されている。しかし、近年更なる印刷速度の高速化が求められており、これでは効果が不十分であり、添加量を増やすと基材密着性の低下などの弊害を引き起こす。 Patent Document 1 proposes a method using palm alkylbisbis (hydroxyethyl) methyl nitrate and palmalkylbis (hydroxyethyl) methyl chloride as a measure to prevent beard misting. However, in recent years, a further increase in printing speed has been demanded, and this is insufficient in effect, and an increase in the amount added causes problems such as a decrease in substrate adhesion.
また特許文献2には4級アンモニウム塩化合物(硫酸塩)を用いた印刷インキをプラスチックフィルムに印刷しフィルムの帯電防止性を付与する提案の中で、印刷時のヒゲや泳ぎの発生を防止するとの記述がある。また特許文献3には脂肪酸ジメチルアンモニゥムエトサルフェートとポリオキシエチレンアルキルエーテルとの混合組成物を用いた裏刷りウレタン型グラビアインキでプラスチックフィルムの帯電防止をする提案がなされている。しかし4級アンモニウム塩化合物(硫酸塩)を用いるとインキの経時安定性が悪くなる問題があった。 Patent Document 2 proposes that printing ink using a quaternary ammonium salt compound (sulfate) is printed on a plastic film to impart antistatic properties to the film. There is a description. Further, Patent Document 3 proposes to prevent the plastic film from being charged with a back-printed urethane gravure ink using a mixed composition of fatty acid dimethyl ammonium methosulfate and polyoxyethylene alkyl ether. However, when a quaternary ammonium salt compound (sulfate) is used, there is a problem that the temporal stability of the ink is deteriorated.
本発明は、上記問題点を解決するものであり、グラビア印刷インキに関し、より詳しくはグラビアインキ印刷時に発生する静電気による印刷不良を低減させることができ、その他物性にも影響を及ぼさないグラビア印刷インキを提供することを目的とする。 The present invention solves the above-described problems, and relates to gravure printing ink, and more specifically, gravure printing ink that can reduce defective printing due to static electricity generated during gravure ink printing and does not affect other physical properties. The purpose is to provide.
本発明の溶剤型グラビア印刷インキは、ポリウレタン樹脂を主バインダーとし、4級アンモニウム塩である塩化モノアルキルベンジルジメチルアンモニウム又は塩化ジアルキルジメチルアンモニウムを含有し、バインダーとして塩化ビニル−酢酸ビニル共重合体を併用した溶剤型グラビア印刷インキである。
また、4級アンモニウム塩を、インキ100重量部に対して0.05〜2.5重量部含有することを特徴とする溶剤型グラビア印刷インキである。
The solvent-type gravure printing ink of the present invention contains a polyurethane resin as a main binder and contains a quaternary ammonium salt monoalkylbenzyldimethylammonium chloride or dialkyldimethylammonium chloride, and a vinyl chloride-vinyl acetate copolymer is used as a binder. Solvent type gravure printing ink.
The solvent-type gravure printing ink further comprises 0.05 to 2.5 parts by weight of a quaternary ammonium salt with respect to 100 parts by weight of the ink.
本発明により、グラビアインキ印刷時に発生する静電気による印刷不良を低減させることができ、さらにインキ経時安定性、印刷フィルムへの接着性、印刷物を巻き取り時のブロッキング性、ラミネート物のボイル適性などを低下させることがないグラビア印刷インキが得られた。 According to the present invention, printing defects due to static electricity generated during gravure ink printing can be reduced, and further, ink aging stability, adhesion to a printing film, blocking property when winding a printed material, boilability of a laminate, etc. A gravure printing ink that does not decrease was obtained.
本発明の詳細について説明する。なお以下の説明で用いる「インキ」とは全て「グラビアインキ」を示す。なお、以下の記述の「部」は「重量部」、「%」は「重量%」を表す。 Details of the present invention will be described. “Ink” used in the following description means “gravure ink”. In the following description, “part” represents “part by weight” and “%” represents “% by weight”.
(ウレタン)
ポリウレタン樹脂としては、従来公知の方法、例えば、特開昭62−153366号公報、特開昭62−153367号公報、特開平1−236289号公報、特開平2−64173号公報、特開平2−64174号公報、特開平2−64175号公報などに開示されている方法により得ることができる。ここでポリウレタン樹脂とは、ポリウレタン樹脂およびポリウレタンウレア樹脂の総称である。
(Urethane)
Examples of the polyurethane resin include conventionally known methods such as JP-A-62-153366, JP-A-62-153367, JP-A-1-236289, JP-A-2-64173, and JP-A-2- 64174, JP-A-2-64175 and the like. Here, the polyurethane resin is a general term for a polyurethane resin and a polyurethane urea resin.
具体的には、ポリオールとジイソシアネート化合物とをイソシアネート基が過剰となる割合で反応させ、末端イソシアネート基のプレポリマーを得、得られるプレポリマーを、適当な溶剤中、すなわち、ノントルエン系グラビアインキ用の溶剤で通常用いられる、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤;メタノール、エタノール、イソプロピルアルコール、n−ブタノールなどのアルコール系溶剤;メチルシクロヘキサン、エチルシクロヘキサンなどの炭化水素系溶剤;あるいはこれらの混合溶剤の中で、鎖伸長剤および/または末端封鎖剤と反応させる二段法、あるいはポリオール、ジイソシアネート化合物、鎖伸長剤および/または末端封鎖剤を上記のうち適切な溶剤中で一度に反応させる一段法により製造される。これらの方法のなかでも、均一なポリウレタン樹脂を得るには、二段法によることが好ましい。ポリウレタン樹脂を二段法で製造する場合、一段目の反応でイソシアネート基と水酸基の当量比は3/1〜1.2/1が好ましく、より好ましくは2.5/1〜1.5/1である。また、鎖伸長剤および/または末端封鎖剤のアミノ基の合計(当量比)が1/0.9〜1.3の割合になるように反応させることが好ましい。イソシアネート基とアミノ基との当量比が1/1.3より小さいときは、鎖伸長剤および/または末端封鎖剤が未反応のまま残存し、ポリウレタン樹脂が黄変したり、印刷後臭気が発生したりする場合がある。ポリオールとしてはポリエステルポリオールが好ましく、ポリエーテルポリオールでは基材密着性や耐ブロッキング性、ボイル適性が劣る傾向がある。 Specifically, a polyol and a diisocyanate compound are reacted in an excess ratio of isocyanate groups to obtain a prepolymer of a terminal isocyanate group, and the resulting prepolymer is used in a suitable solvent, that is, for non-toluene gravure ink. Ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol; Hydrocarbon-based solvents such as methylcyclohexane, ethylcyclohexane, etc .; or a mixed solvent thereof in a two-stage method in which it is reacted with a chain extender and / or end-capping agent, or polyol, diisocyanate compound, chain extender and / or The end capping agent is produced by one-step process of reacting at a time in a suitable solvent of the above. Among these methods, it is preferable to use a two-stage method in order to obtain a uniform polyurethane resin. When a polyurethane resin is produced by a two-stage method, the equivalent ratio of isocyanate groups to hydroxyl groups is preferably 3/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1 in the first stage reaction. It is. Moreover, it is preferable to make it react so that the total (equivalent ratio) of the amino group of a chain extender and / or a terminal blocker may become a ratio of 1 / 0.9-1.3. When the equivalent ratio of isocyanate group to amino group is less than 1 / 1.3, the chain extender and / or end-capping agent remains unreacted, the polyurethane resin turns yellow, and odor occurs after printing There is a case to do. Polyester polyol is preferable as the polyol, and polyether polyol tends to be inferior in substrate adhesion, blocking resistance, and boil suitability.
このようにして得られるポリウレタン樹脂の重量平均分子量は、15,000〜100,000の範囲内とすることが好ましい。ポリウレタン樹脂の重量平均分子量が15,000未満の場合には、得られるインキの組成物の耐ブロッキング性、印刷被膜の強度や耐油性などが低くなる傾向があり、100,000を超える場合には、得られるインキ組成物の粘度が高くなり、印刷被膜の光沢が低くなる傾向がある。ウレタン樹脂量は有効成分でインキ100部中に3〜30部が好ましい。より好ましくは6〜21部である。 The weight average molecular weight of the polyurethane resin thus obtained is preferably in the range of 15,000 to 100,000. When the weight average molecular weight of the polyurethane resin is less than 15,000, there is a tendency that the blocking resistance of the ink composition obtained, the strength of the printed film, the oil resistance, and the like tend to be low. The viscosity of the resulting ink composition tends to increase, and the gloss of the printed film tends to decrease. The amount of urethane resin is an active ingredient and is preferably 3 to 30 parts in 100 parts of ink. More preferably, it is 6-21 parts.
(4級アンモニウム塩)
本発明で用いられる4級アンモニウム塩としては、塩化モノアルキルトリメチルアンモニウム(塩化セチルトリメチルアンモニウム、塩化ココアルキルトリメチルアンモニウム、塩化ステアリルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウムなど)、塩化モノアルキルベンジルジメチルアンモニウム(塩化ココベンジルジメチルアンモニウム、塩化ヤシベンジルジメチルアンモニウム、塩化テトラデシルベンジルジメチルアンモニウムなど)、塩化ジアルキルジメチルアンモニウム(塩化ジデシルジメチルアンモニウム、塩化ジココイルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化ジオレイルジメチルアンモニウムなど)等が挙げられるが、これらに限定されるものではない。好ましくは塩化モノアルキルトリメチルアンモニウム、塩化モノアルキルベンジルジメチルアンモニウム、塩化ジアルキルジメチルアンモニウムである。更に好ましくは塩化モノアルキルベンジルジメチルアンモニウムである。4級アンモニウム塩は有効成分としてインキ100部に対して0.05〜2.5部使用するのが好ましい。0.05部以下だと静電気による印刷不良を低減させる効果が少なく、2.5部以上だと基材への密着を低下させる恐れがある。
(Quaternary ammonium salt)
Examples of the quaternary ammonium salt used in the present invention include monoalkyltrimethylammonium chloride (such as cetyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride), monoalkylbenzyldimethylammonium chloride (coconut chloride). Benzyl dimethyl ammonium, coconut benzyl dimethyl ammonium chloride, tetradecyl benzyl dimethyl ammonium chloride, etc.), dialkyl dimethyl ammonium chloride (didecyl dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dioleyl dimethyl ammonium chloride, etc.), etc. However, it is not limited to these. Preferred are monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, and dialkyldimethylammonium chloride. More preferred is monoalkylbenzyldimethylammonium chloride. The quaternary ammonium salt is preferably used as an active ingredient in an amount of 0.05 to 2.5 parts with respect to 100 parts of ink. If it is 0.05 parts or less, there is little effect of reducing printing defects due to static electricity, and if it is 2.5 parts or more, adhesion to the substrate may be reduced.
(塩化ビニル−酢酸ビニル共重合体)
塩化ビニル−酢酸ビニル共重合体の樹脂は、塩化ビニルと酢酸ビニルのモル比、重合度、分子量により、耐薬品性、強靭性、接着性、溶解性等が変わる。なお、インキの種類、印刷方法、印刷構成等から適宜塩酢ビ樹脂を選択することができる。市販の塩酢ビ樹脂としては、例えばSOLBIN C,CL、CH,CN、C5R,A,AL,TA2,TA3,TAO,TA5R、M、ME,MFK(日信化学工業株式会社製)、VINNOLE14/45,H14/36,H40/55,E15/45M(WACKER社製)等が挙げられるが、これらに限定されるものではない。塩化ビニル−酢酸ビニル共重合体樹脂を添加することにより耐ブロッキング性が向上する。樹脂添加量としては有効成分でインキ100重量部に対して0.2〜24重量部が好ましい。
(Vinyl chloride-vinyl acetate copolymer)
The resin of vinyl chloride-vinyl acetate copolymer varies in chemical resistance, toughness, adhesiveness, solubility, etc. depending on the molar ratio of vinyl chloride and vinyl acetate, the degree of polymerization, and the molecular weight. In addition, a vinyl acetate resin can be selected suitably from the kind of ink, a printing method, a printing structure, etc. Examples of commercially available vinyl chloride resin include SOLBIN C, CL, CH, CN, C5R, A, AL, TA2, TA3, TAO, TA5R, M, ME, MFK (manufactured by Nissin Chemical Industry Co., Ltd.), VINNOLE14 / 45, H14 / 36, H40 / 55, E15 / 45M (manufactured by WACKER) and the like, but are not limited thereto. The blocking resistance is improved by adding a vinyl chloride-vinyl acetate copolymer resin. The amount of resin added is preferably 0.2 to 24 parts by weight with respect to 100 parts by weight of ink as an active ingredient.
本発明のグラビア印刷インキのバインダー樹脂にはポリウレタン樹脂、塩化ビニル−酢酸ビニル共重合体の他にアクリル樹脂、アクリル変性ウレタン樹脂、スチレン/アクリル
樹脂、エチレン/アクリル樹脂、ポリエステル樹脂、ロジン変性マレイン酸樹脂、ポリビニルアセタール樹脂、ポリアマイド樹脂、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロース等のセルロース系樹脂等を併用することができる。
The binder resin of the gravure printing ink of the present invention includes acrylic resin, acrylic modified urethane resin, styrene / acrylic in addition to polyurethane resin and vinyl chloride-vinyl acetate copolymer.
Resin, ethylene / acrylic resin, polyester resin, rosin-modified maleic acid resin, polyvinyl acetal resin, polyamide resin, cellulose resin such as hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose and the like can be used in combination.
本発明のグラビア印刷インキに必要とされる機能を有するために配合される着色剤としては、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 NoYellow83を用いることが好ましい。 Examples of the colorant blended to have the function required for the gravure printing ink of 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, isoindoline, etc. Pigments. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. Pigment NoYellow83 is preferably used.
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、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。アルミニウムは粉末またはペースト状であるが、取扱い性および安全性の面からペースト状で使用するのが好ましく、リーフィングまたはノンリーフィングを使用するかは輝度感および濃度の点から適宜選択される。グラビア印刷方式で裏刷り印刷する場合、最初に墨インキが印刷されることが多く、ヒゲやミスチングが起こり易いと言われている。本発明の溶剤型グラビア印刷インキは墨インキで優れた効果を発揮するが、特に色相に制限はない。 Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, 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. Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration. When back printing is performed by a gravure printing method, black ink is often printed first, and it is said that beard and misting are likely to occur. The solvent-type gravure printing ink of the present invention exhibits an excellent effect with black ink, but there is no particular limitation on the hue.
着色剤はインキの濃度・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%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種以上を併用して用いることができる。 It is preferable that the colorant is contained in an amount sufficient to ensure the density and coloring power of the ink, that is, 1 to 50% of the total weight of the ink. Moreover, a coloring agent can be used individually or in combination of 2 or more types.
顔料を有機溶剤に安定に分散させるには、前記樹脂単独でも分散可能であるが、さらに顔料を安定に分散するため分散剤を併用することもできる。分散剤としては、アニオン性、ノニオン性、カチオン性、両イオン性などの界面活性剤を使用することができる。分散剤は、インキの保存安定性の観点からインキの総重量に対して0.05%以上、ラミネート適性の観点から5%以下でインキ中に含まれることが好ましく、さらに好ましくは、0.1〜2%の範囲である。 In order to stably disperse the pigment in the organic solvent, it is possible to disperse the resin alone, but it is also possible to use a dispersant in order to disperse the pigment stably. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The dispersant is preferably contained in the ink in an amount of 0.05% or more based on the total weight of the ink from the viewpoint of the storage stability of the ink and 5% or less from the viewpoint of the suitability for lamination, and more preferably 0.1%. It is in the range of ˜2%.
本発明のグラビア印刷インキは、樹脂、着色剤などを有機溶剤中に溶解および/または分散することにより製造することができる。具体的には、顔料をポリウレタン樹脂により有機溶剤に分散させた顔料分散体を製造し、得られた顔料分散体に必要に応じて他の化合物などを配合することにより、インキを製造することができる。 The gravure printing ink of the present invention can be produced by dissolving and / or dispersing a resin, a colorant and the like in an organic solvent. Specifically, it is possible to produce a pigment dispersion in which a pigment is dispersed in an organic solvent with a polyurethane resin, and to produce an ink by blending the obtained pigment dispersion with other compounds as necessary. it can.
顔料分散体における顔料の粒度分布は、分散機の粉砕メディアのサイズ、粉砕メディアの充填率、分散処理時間、顔料分散体の吐出速度、顔料分散体の粘度などを適宜調節することにより、調整することができる。分散機としては一般に使用される、例えばローラーミル、ボールミル、ペブルミル、アトライター、サンドミルなどを用いることができる。 The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.
インキ中に気泡や予期せずに粗大粒子などが含まれる場合は、印刷物品質を低下させるため、濾過などにより取り除くことが好ましい。濾過器は従来公知のものを使用することができる。 In the case where bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.
前記方法で製造されたインキ粘度は、顔料の沈降を防ぎ、適度に分散させる観点から10mPa・s以上、インキ製造時や印刷時の作業性効率の観点から1000mPa・s以下の範囲であることが好ましい。なお、上記粘度はトキメック社製B型粘度計で25℃において測定された粘度である。 The ink viscosity produced by the above method is in the range of 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. preferable. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
インキの粘度は、使用される原材料の種類や量、例えば樹脂、着色剤、有機溶剤などを適宜選択することにより調整することができる。また、インキ中の顔料の粒度および粒度分布を調節することによりインキの粘度を調整することもできる。 The viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, resin, colorant, organic solvent, and the like. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.
有機溶剤としては、前述のポリウレタン樹脂の合成に用いられた溶剤が使用でき、メタノール、エタノール、n−プロパノール、イソプロパノール、ブタノールなどのアルコール系有機溶剤、アセトン,メチルエチルケトン、メチルイソブチルケトンなどのケトン系有機溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系有機溶剤、n−ヘキサン、n−ヘプタン、n−オクタンなどの脂肪族炭化水素系有機溶剤、およびシクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロヘプタン、シクロオクタンなどの脂環族炭化水素系有機溶剤、トルエンなどの芳香族炭化水素系有機溶剤が挙げることができ、バインダー樹脂の溶解性や乾燥性などを考慮して、混合して利用することが好ましい。これらの有機溶剤の使用量としては、通常のインキでは30重量%以上含有される。本発明の静電気による印刷不良を低減させるにはアルコール系有機溶剤やケトン系有機溶剤などの極性の高い有機溶剤を選定するのが好ましい。印刷時のインキ溶剤組成でケトン系有機溶剤またはアルコール系有機溶剤または両者の合計が10〜100%が好ましい。更に好ましくは25〜100%である。 As the organic solvent, the solvents used for the synthesis of the above-mentioned polyurethane resin can be used. Alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol, and ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, n-octane, and cyclohexane, methylcyclohexane, ethylcyclohexane, Examples include cycloaliphatic hydrocarbon organic solvents such as cycloheptane and cyclooctane, and aromatic hydrocarbon organic solvents such as toluene, and are used by mixing in consideration of the solubility and drying properties of the binder resin. It is preferable to do. The amount of these organic solvents used is 30% by weight or more in ordinary ink. In order to reduce printing defects due to static electricity of the present invention, it is preferable to select an organic solvent having a high polarity such as an alcohol-based organic solvent or a ketone-based organic solvent. The ink solvent composition at the time of printing is preferably 10 to 100% of the ketone organic solvent or the alcohol organic solvent or the total of both. More preferably, it is 25 to 100%.
4級アンモニウム塩を含有させる方法としては、インキ製造時に配合する、インキ使用直前に添加する、あるいは、希釈溶剤で印刷に適した粘度に希釈した後の希釈インキに添加するなどの方法がある。4級アンモニウム塩の含有量は、インキ(ベースインキ)を基準とするか、希釈インキを基準として計算を行うかにより値が変化する。本発明においては、インキ(ベースインキ)を基準として含有量の計算を行なっている。
インキあるいは稀釈インキに添加する場合は、秤量精度の点からアルコール、メチルエチルケトンなどの有機溶剤で稀釈して、5部濃度の稀釈溶液で添加するのが望ましい。
As a method of containing a quaternary ammonium salt, there are a method of blending at the time of ink production, adding immediately before using the ink, or adding to a diluted ink after diluting to a viscosity suitable for printing with a diluent solvent. The content of the quaternary ammonium salt varies depending on whether the calculation is based on the ink (base ink) or the diluted ink. In the present invention, the content is calculated based on the ink (base ink).
When added to ink or diluted ink, it is desirable to dilute with an organic solvent such as alcohol or methyl ethyl ketone and add it as a 5-part diluted solution from the viewpoint of weighing accuracy.
本発明の溶剤型グラビア印刷インキを含んだ印刷インキは、グラビア印刷の他、フレキソ印刷などの既知の印刷方式に用いることができ、各種プラスチックフィルム等の被着体に印刷することができる。具体的に、印刷可能なプラスチックフィルムとしては、ポリエチレン、ポリプロピレンなどの延伸および無延伸ポリオレフィン、ポリエステル、ナイロン、セロファン、ビニロンなどを挙げることができる。
また、グラビア印刷の場合、グラビア印刷に適した粘度及び濃度にまで希釈溶剤で希釈され、単独でまたは混合されて各印刷ユニットに供給される。
The printing ink containing the solvent-type gravure printing ink of the present invention can be used for known printing methods such as flexographic printing in addition to gravure printing, and can be printed on adherends such as various plastic films. Specifically, examples of the printable plastic film include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon.
In the case of gravure printing, it is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed.
更に、この印刷物の印刷面にイミン系、イソシアネート系、ポリブタジエン系、チタン系等の各種アンカーコート剤を介して、溶融ポリエチレン樹脂を積層する通常のエクストルージョンラミネート(押し出しラミネート)法、印刷面にウレタン系等の接着剤を塗工し、プラスチックフィルムを積層するドライラミネート法、印刷面に直接溶融ポリプロピレンを圧着して積層するダイレクトラミネート法等、公知のラミネート工程により、ラミネート積層物も得ることができる。 Furthermore, the usual extrusion lamination (extrusion laminating) method in which molten polyethylene resin is laminated on the printed surface of the printed material through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printed surface Laminate laminates can also be obtained by a known laminating process such as a dry laminating method in which an adhesive such as a coating is applied and a plastic film is laminated, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on a printing surface. .
以下、実施例をあ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。アミン価は、樹脂1g中に含有するアミノ基を中和するのに必要とする塩酸に当量の水酸化カリウムのmg数である。アミン価の測定方法については、下記の通りである。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. The amine value is the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The method for measuring the amine value is as follows.
[アミン価の測定方法]
試料を0.5〜2g精秤する。(試料量:Sg)精秤した試料に中性エタノール(BDG中性)30mLを加え溶解させる。得られた溶液を0.2mol/Lエタノール性塩酸溶液(力価:f)で滴定を行なう。溶液の色が緑から黄に変化した点を終点とし、この時の滴定量A(mL)を用い次の式によりアミン価を求めた。
アミン価=(A×f×0.2×56.108)/S
粘度はトキメック社製B型粘度計で25℃において測定した。
分子量はGPC(ゲルパーミエーションクロマトグラフィー)装置を用いて分子量分布を測定し、ポリスチレン換算分子量として求めた。
[Method for measuring amine value]
Weigh 0.5-2 g of sample accurately. (Sample amount: Sg) 30 mL of neutral ethanol (BDG neutral) is added to a precisely weighed sample and dissolved. The obtained solution is titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined by the following formula using the titration amount A (mL) at this time.
Amine number = (A × f × 0.2 × 56.108) / S
The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.
The molecular weight was determined as a polystyrene-converted molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus.
<ポリウレタンワニスの調整>
〔合成例1〕
アジピン酸とプロピレングリコールから得られる数平均分子量(以下Mnという)2000のポリエステルジオール(PPA2000)229.4部、イソホロンジイソシアネート51部および酢酸エチル200.0部を窒素気流下に85℃で4時間反応させ、末端イソシアネートプレポリマーの溶剤溶液480.4部を得た。次いでイソホロンジアミン19.5部、ジ−n−ブチルアミン0.09部、酢酸エチル250.0部およびイソプロピルアルコール250.0部を混合したものに、得られた末端イソシアネートプレポリマーの溶剤溶液483.7部を室温で徐々に添加し、次に50℃で1時間反応させ、固形分30%、重量平均分子量33000、アミン価5.0 mgKOH/樹脂1g、25℃における粘度400mPa・sのポリウレタン樹脂(ワニスA)を得た。
<Adjustment of polyurethane varnish>
[Synthesis Example 1]
229.4 parts of polyester diol (PPA2000) having a number average molecular weight (hereinafter referred to as Mn) of 2000 obtained from adipic acid and propylene glycol, 51 parts of isophorone diisocyanate and 200.0 parts of ethyl acetate were reacted at 85 ° C. for 4 hours under a nitrogen stream. 480.4 parts of a solvent solution of a terminal isocyanate prepolymer was obtained. Subsequently, 19.5 parts of isophoronediamine, 0.09 part of di-n-butylamine, 250.0 parts of ethyl acetate and 250.0 parts of isopropyl alcohol were mixed with a solvent solution 483.7 of the obtained terminal isocyanate prepolymer. Parts are gradually added at room temperature, and then reacted at 50 ° C. for 1 hour. A polyurethane resin having a solid content of 30%, a weight average molecular weight of 33,000, an amine value of 5.0 mgKOH / resin, and a viscosity of 400 mPa · s at 25 ° C. Varnish A) was obtained.
〔合成例2〕
PPA2000 114.7部、Mn2000のポリプロピレングリコール(PPG2000)114.7部、イソホロンジイソシアネート51.1部および酢酸エチル125.0部を窒素気流下に85℃で4時間反応させ、末端イソシアネートプレポリマーの溶剤溶液405.4部を得た。次いでイソホロンジアミン19.6部、ジ−n−ブチルアミン0.09部、酢酸エチル307部およびイソプロピルアルコール270部を混合したものに、得られた末端イソシアネートプレポリマーの溶剤溶液405.4部を室温で徐々に添加し、次に50℃で1時間反応させ、固形分30%、重量平均分子量35000、アミン価6.0 mgKOH/樹脂1g、25℃における粘度350mPa・sのポリウレタン樹脂(ワニスB)を得た。
[Synthesis Example 2]
114.7 parts of PPA2000, 114.7 parts of polypropylene glycol (PPG2000) of Mn2000, 51.1 parts of isophorone diisocyanate and 125.0 parts of ethyl acetate were reacted at 85 ° C. for 4 hours under a nitrogen stream, and the solvent for the terminal isocyanate prepolymer 405.4 parts of solution were obtained. Next, 19.6 parts of isophoronediamine, 0.09 part of di-n-butylamine, 307 parts of ethyl acetate and 270 parts of isopropyl alcohol were mixed with 405.4 parts of the solvent solution of the obtained terminal isocyanate prepolymer at room temperature. Gradually added, then reacted at 50 ° C. for 1 hour, and a polyurethane resin (varnish B) having a solid content of 30%, a weight average molecular weight of 35000, an amine value of 6.0 mg KOH / resin, and a viscosity of 350 mPa · s at 25 ° C. Obtained.
<塩化ビニル−酢酸ビニル共重合体ワニスの調製>
〔調整例1〕
塩化ビニル−酢酸ビニル共重合体(重合度300、数平均分子量22000、Tg76℃[ソルバインAL、日信化学工業(株)製])24部を、酢酸エチル76部に混合溶解させて、ワニスCを得た。
<Preparation of vinyl chloride-vinyl acetate copolymer varnish>
[Adjustment Example 1]
24 parts of vinyl chloride-vinyl acetate copolymer (degree of polymerization 300, number average molecular weight 22000, Tg 76 ° C. [Solvine AL, manufactured by Nissin Chemical Industry Co., Ltd.]) were mixed and dissolved in 76 parts of ethyl acetate, and varnish C Got.
<ポリアミドワニスの調整>
〔 調整例2〕
軟化点が112℃〜120℃であるポリアミド樹脂(レオマイドS−2800 花王(株)製)30部をメチルシクロヘキサン50部、イソプロピルアルコール20部に混合溶解させて、ワニスDを得た。
<Adjustment of polyamide varnish>
[Example of adjustment 2]
Varnish D was obtained by mixing and dissolving 30 parts of a polyamide resin having a softening point of 112 ° C. to 120 ° C. (Rheamide S-2800, manufactured by Kao Corporation) in 50 parts of methylcyclohexane and 20 parts of isopropyl alcohol.
<ニトロセルロースワニスの調整>
〔調整例3〕
ニトロセルロース(NC RS−2 KCNC、KOREA CNC LTD製)20部を、酢酸エチル26部とイソプロピルアルコール20部、メチルシクロヘキサン34部に混合溶解させて、ワニスEを得た。
<Adjustment of nitrocellulose varnish>
[Adjustment Example 3]
Varnish E was obtained by mixing and dissolving 20 parts of nitrocellulose (NC RS-2 KCNC, manufactured by KOREA CNC LTD) in 26 parts of ethyl acetate, 20 parts of isopropyl alcohol, and 34 parts of methylcyclohexane.
<参考実施例1>
得られたポリウレタン樹脂(ワニスA)40部、塩化ビニル−酢酸ビニル樹脂(ワニスC)15部、カーボンブラック10部(Printex25、デグサ社製)、酢酸エチル10部、メチルエチルケトン15部、イソプロピルアルコール10の混合物を練肉し、練肉後、4級アンモニウム塩A(コータミン24P、有効成分27%、花王(株)製)1.1部添加しインキ1を得た。
下表1に示した配合比で実施例2〜7、比較例1〜4を同様の方法で作成しインキ2〜11を得た。なお、実施例6は、参考実施例6である。
<Reference Example 1>
40 parts of the obtained polyurethane resin (varnish A), 15 parts of vinyl chloride-vinyl acetate resin (varnish C), 10 parts of carbon black (Printex25, manufactured by Degussa), 10 parts of ethyl acetate, 15 parts of methyl ethyl ketone, 10 of isopropyl alcohol The mixture was kneaded, and after kneading, 1.1 parts of quaternary ammonium salt A (Cotamine 24P, active ingredient 27%, manufactured by Kao Corporation) was added to obtain ink 1.
Examples 2 to 7 and Comparative Examples 1 to 4 were prepared in the same manner at the compounding ratios shown in Table 1 below, and inks 2 to 11 were obtained. Note that Example 6 is Reference Example 6.
(参考)4級アンモニウム塩A:コータミン24P、塩化ラウリルトリメチルアンモニウム、有効成分27%、花王(株)製
4級アンモニウム塩B:サニゾールC、塩化アルキル(C12〜16)ベンジルジメチルアンモニウム、有効成分50%、花王(株)製
4級アンモニウム塩C:コータミンD86P、塩化ジステアリルジメチルアンモニウム、有効成分75%、花王(株)製
4級アンモニウム塩D:エソガードC/12、塩化アルキル(C8〜18)ビス(2ヒドロキシエチル)メチルアンモニウム、有効成分75%、ライオン(株)製
4級アンモニウム塩E:アーカード 2HT-50ES、硫化ジ硬化牛脂アルキル(C16〜18)エチルメチルアンモニウム、有効成分50%、ライオン(株)製
フタロシアニンブルー:リオノ−ルブル−KLH 東洋インキ製造(株)製
(Reference) Quaternary ammonium salt A: Cotamine 24P, lauryltrimethylammonium chloride, active ingredient 27%, quaternary ammonium salt B: Sanisole C, alkyl chloride (C12-16) benzyldimethylammonium, active ingredient 50 %, Kao Co., Ltd. quaternary ammonium salt C: Cotamine D86P, distearyldimethylammonium chloride, 75% active ingredient, Kao Co., Ltd. quaternary ammonium salt D: Esogard C / 12, alkyl chloride (C8-18) Bis (2hydroxyethyl) methylammonium, active ingredient 75%, quaternary ammonium salt E: Lion Card 2HT-50ES, di-cured beef tallow alkyl (C16-18) ethylmethylammonium, active ingredient 50%, Lion Phthalocyanine Blue, manufactured by: Lionol Blue-KLH Toyo Ink Manufactured by
実施例2〜7、参考実施例1及び比較例1〜4で得られたインキについて、下記の方法で静電気障害試験、経時安定性試験、基材密着性試験、耐ブロッキング性試験、ボイル適性を評価した。インキ1〜11を印刷時の粘度に調整するため、トルオール50部、酢酸エチル30部、イソプロピルアルコール20部からなる混合溶剤を用いて、25℃においてザーンカップNo3で測定した粘度が16秒となるように希釈し、希釈インキ1〜11を得た。 For the inks obtained in Examples 2 to 7, Reference Example 1 and Comparative Examples 1 to 4, the following methods were used to determine the electrostatic failure test, stability with time test, substrate adhesion test, blocking resistance test, and boil suitability. evaluated. In order to adjust the inks 1 to 11 to the viscosity at the time of printing, using a mixed solvent consisting of 50 parts of toluene, 30 parts of ethyl acetate and 20 parts of isopropyl alcohol, the viscosity measured with Zaan Cup No. 3 at 25 ° C. is 16 seconds. Dilution inks 1 to 11 were obtained.
〔静電気障害試験〕
希釈インキ1〜11を使用して、版深5μm〜45μmのグラビアグラデーション版(5μm刻みで彫刻)を備えたグラビア印刷機により、厚さ20μmの内面コロナ放電処理有り、帯電防止処理無し、ポリプロピレンフィルム「ECO-BQ」(フタムラ化学(株)製)に印刷速度120m/分、乾燥器温度40℃〜50℃で30秒間連続印刷し、印刷フィルムを得た。
得られた印刷フィルムの、45μm印刷部の静電気障害(ヒゲ、ミスチング)の発生状態を評価した。
◎:静電気障害の発生がまったくない
○:静電気障害の発生が殆どない。
△:若干静電気障害の発生がある。
×:著しく静電気障害が発生する。
実用レベルは○以上である。
[Electrostatic failure test]
Using dilution ink 1-11, gravure printing machine equipped with gravure gradation plate (engraving in 5μm increments) with plate depth of 5μm to 45μm, inner corona discharge treatment with thickness of 20μm, no antistatic treatment, polypropylene film A printing film was obtained by continuously printing “ECO-BQ” (manufactured by Futamura Chemical Co., Ltd.) at a printing speed of 120 m / min and a dryer temperature of 40 ° C. to 50 ° C. for 30 seconds.
The state of occurrence of static electricity damage (whiskering and misting) in the 45 μm printing part of the obtained printing film was evaluated.
A: There is no occurrence of electrostatic failure. O: Almost no occurrence of electrostatic failure.
Δ: Slightly static failure occurred.
X: Electrostatic failure occurs remarkably.
The practical level is more than ○.
〔経時安定性試験〕
インキ1〜11を40℃の恒温室で1週間静置した後に、安定性を評価した。
○:増粘、沈殿、分離が見られない。
△:僅かな増粘または僅かな沈殿または僅かな分離が見られる。
×:増粘または沈殿または分離が見られる。
実用レベルは△以上である。
[Stability test over time]
The inks 1 to 11 were allowed to stand in a constant temperature room at 40 ° C. for 1 week, and then the stability was evaluated.
○: No thickening, precipitation, or separation is observed.
Δ: Slight thickening or slight precipitation or slight separation is observed.
X: Thickening or precipitation or separation is observed.
The practical level is Δ or more.
〔基材密着性試験〕
希釈インキ1〜11を使用して、版深5μm〜45μmのグラビアグラデーション版(5μm刻みで彫刻)を備えたグラビア印刷機により、厚さ20μmの内面コロナ放電処理有り、ポリプロピレンフィルム「パイレンP2161」(東洋紡績(株)製)と蒸着PET「GLARH」(凸版印刷(株)製)に印刷速度40m/分、乾燥器温度50℃で30秒間連続印刷し、印刷フィルムを得た。
得られた印刷物の35μm部分にセロハンテープ(ニチバン製、幅12mm)を貼り付け親指で5回強く擦った後、セロハンテープを徐々に引き離し途中から、急激に引き離してインキ皮膜の剥離の程度を調べた。インキがセロハンテープに転移する状態を評価をした。
○:セロハンテープにインキが100%転移しない
△:急激に引き離したセロハンテープ部分にインキが10%程度転移するが、ゆっくり引き剥がした部分は100%転移しない。
×:セロハンテープを張った部分が50%以上転移する
実用レベルは△以上である。
[Base material adhesion test]
Using dilution ink 1-11, gravure printing machine equipped with gravure gradation plate (engraving in 5 μm increments) with a plate depth of 5 μm to 45 μm, inner corona discharge treatment with a thickness of 20 μm, polypropylene film “Pyrene P2161” ( Toyobo Co., Ltd.) and vapor-deposited PET “GLARAH” (manufactured by Toppan Printing Co., Ltd.) were continuously printed at a printing speed of 40 m / min and a dryer temperature of 50 ° C. for 30 seconds to obtain a printing film.
Apply cellophane tape (Nichiban, width 12 mm) to the 35 μm portion of the printed matter and rub it strongly with the thumb 5 times. It was. The state in which the ink was transferred to the cellophane tape was evaluated.
◯: The ink does not transfer 100% to the cellophane tape. Δ: The ink transfers about 10% to the cellophane tape portion that is abruptly separated, but the portion that is slowly peeled off does not transfer 100%.
X: The practical level at which the portion where the cellophane tape is stretched is transferred by 50% or more is Δ or more.
〔耐ブロッキング性試験〕
希釈インキ1〜11を使用して、版深5μm〜45μmのグラビアグラデーション版(5μm刻みで彫刻)を備えたグラビア印刷機により、厚さ20μmの内面コロナ放電処理有り、ポリプロピレンフィルム「パイレンP2161」(東洋紡績(株)製)に印刷速度40m/分、乾燥器温度50℃で30秒間連続印刷し、印刷フィルムを得た。
印刷物と同じ大きさに切ったOPPフィルム未処理面と印刷面とを重ね合わせて、5kg/cm2の荷重をかけ、40℃80%RHの雰囲気で24時間放置後、印刷面と未処理OPPフィルムを引き剥がし、インキの剥離の程度から耐ブロッキング性を評価した。
○:インキが全く剥離しなかったもの。
△:インキがフィルムから剥離した面積が20〜50%のもの。
×:インキがフィルムから剥離した面積が50%を超えるもの。
実用レベルは○以上である。
[Blocking resistance test]
Using dilution ink 1-11, gravure printing machine equipped with gravure gradation plate (engraving in 5 μm increments) with a plate depth of 5 μm to 45 μm, inner corona discharge treatment with a thickness of 20 μm, polypropylene film “Pyrene P2161” ( Toyobo Co., Ltd.) was continuously printed at a printing speed of 40 m / min and a dryer temperature of 50 ° C. for 30 seconds to obtain a printed film.
The untreated surface of the OPP film cut to the same size as the printed material and the printed surface are overlapped, applied with a load of 5 kg / cm 2 , left in an atmosphere of 40 ° C. and 80% RH for 24 hours, and then the printed surface and the untreated OPP The film was peeled off, and blocking resistance was evaluated from the degree of ink peeling.
○: The ink did not peel at all.
(Triangle | delta): The area where the ink peeled from the film is 20 to 50%.
X: The area where the ink peeled from the film exceeded 50%.
The practical level is more than ○.
〔ボイル適性〕
希釈インキ1〜11を使用して、版深30μmのグラビア版を備えたグラビア印刷機により、厚さ15μmの内面コロナ放電処理有り、ナイロンフィルム「エンブレムON−RT」(ユニチカ(株)製)に印刷速度40m/分、乾燥器温度50℃で30秒間連続印刷し、印刷フィルムを得た。
得られた印刷物にポリウレタン系アンカーコート剤「EL510,CAT−RT80」(東洋モートン社製)を塗布し、塗布面上にそれぞれ低密度ポリエチレン(三菱油化社製「ユカロンLK30」およびトーセロ社製「TUX−FCD」厚さ40μm)にてエクストルージョンラミネート加工を行い、ラミネート物を得た。ナイロンフィルムのラミネート物は40℃で2日間エージングした。
得られたナイロンフィルムのラミネート物を、ポリエチレンフィルム側を内側にしてヒートシールし、得られた袋体に内容物として水を充填し、90℃で30分間煮沸した時の外観を目視にて評価した。
○:全く異常のないもの
×:デラミネーションやブリスターを生じたもの
[Boil aptitude]
Using diluted ink 1-11, with a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, with inner corona discharge treatment with a thickness of 15 μm, nylon film “Emblem ON-RT” (manufactured by Unitika Ltd.) Continuous printing was performed at a printing speed of 40 m / min and a dryer temperature of 50 ° C. for 30 seconds to obtain a printed film.
Polyurethane anchor coating agent “EL510, CAT-RT80” (manufactured by Toyo Morton Co., Ltd.) was applied to the obtained printed matter, and low density polyethylene (“Yukaron LK30” manufactured by Mitsubishi Yuka Co., Ltd.) and “ Extrusion laminating was performed with a “TUX-FCD” thickness of 40 μm to obtain a laminate. The nylon film laminate was aged at 40 ° C. for 2 days.
The obtained nylon film laminate was heat-sealed with the polyethylene film side inside, and the resulting bag was filled with water as the contents, and visually evaluated when boiled at 90 ° C. for 30 minutes. did.
○: No abnormality at all ×: Delamination or blister
表2に示すように、4級アンモニウム塩として、塩化モノアルキルベンジルジメチルアンモニウム又は塩化ジアルキルジメチルアンモニウムを用いた実施例2〜7のインキは、静電気障害(ヒゲ、ミスチング)が良好であり、経時安定性、基材密着性、耐ブロッキング性およびボイル適性も良好であった。 As shown in Table 2, the inks of Examples 2 to 7 using monoalkylbenzyldimethylammonium chloride or dialkyldimethylammonium chloride as the quaternary ammonium salt have good electrostatic damage (whisker and misting) and are stable over time. Property, substrate adhesion, blocking resistance and boil suitability were also good.
Claims (2)
さらに、併用樹脂バインダーとして塩化ビニル−酢酸ビニル共重合体を併用したことを特徴とする溶剤型グラビア印刷インキ。 A solvent-type gravure printing ink comprising a polyurethane resin as a main binder and containing a quaternary ammonium salt that is a monoalkylbenzyldimethylammonium chloride or a dialkyldimethylammonium chloride ,
Furthermore, the solvent-type gravure printing ink characterized by using together a vinyl chloride-vinyl acetate copolymer as a combined resin binder.
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