JP6871084B2 - Liquid ink composition - Google Patents
Liquid ink composition Download PDFInfo
- Publication number
- JP6871084B2 JP6871084B2 JP2017124197A JP2017124197A JP6871084B2 JP 6871084 B2 JP6871084 B2 JP 6871084B2 JP 2017124197 A JP2017124197 A JP 2017124197A JP 2017124197 A JP2017124197 A JP 2017124197A JP 6871084 B2 JP6871084 B2 JP 6871084B2
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- liquid ink
- resin
- composition according
- polyurethane
- 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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- 239000007788 liquid Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 65
- 239000000976 ink Substances 0.000 claims description 104
- 229920005989 resin Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 59
- 229920005749 polyurethane resin Polymers 0.000 claims description 32
- 238000007639 printing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 229920003226 polyurethane urea Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229920002396 Polyurea Polymers 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000012860 organic pigment Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000002635 aromatic organic solvent Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000007646 gravure printing Methods 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 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 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000005456 alcohol based solvent Substances 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 240000008415 Lactuca sativa Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000012045 salad Nutrition 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- IVGSTUBCZCNXPB-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol 2,4-dimethylpentane-1,5-diol Chemical compound C(C)C(CO)CC(CO)CC.CC(CO)CC(CO)C IVGSTUBCZCNXPB-UHFFFAOYSA-N 0.000 description 1
- QLSQYTKEUVPIJA-UHFFFAOYSA-N 2-(1-aminopropan-2-ylamino)ethanol Chemical compound NCC(C)NCCO QLSQYTKEUVPIJA-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- XWFCJSXTVSOIDN-UHFFFAOYSA-N 2-propan-2-ylbutane-1,4-diol Chemical compound CC(C)C(CO)CCO XWFCJSXTVSOIDN-UHFFFAOYSA-N 0.000 description 1
- AMUBKBXGFDIMDJ-UHFFFAOYSA-N 3-heptyl-1,2-bis(9-isocyanatononyl)-4-pentylcyclohexane Chemical compound CCCCCCCC1C(CCCCC)CCC(CCCCCCCCCN=C=O)C1CCCCCCCCCN=C=O AMUBKBXGFDIMDJ-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- WWEZICVNSNUPRQ-UHFFFAOYSA-N 5-isocyanato-1-(isocyanomethyl)-1,3,3-trimethylcyclohexane Chemical compound CC1(C)CC(N=C=O)CC(C)(C[N+]#[C-])C1 WWEZICVNSNUPRQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQJLHLZXPOHBW-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(CCl)(CCl)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(CCl)(CCl)C1=CC=CC=C1 WRQJLHLZXPOHBW-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- 229930006000 Sucrose Natural products 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000005021 flexible packaging material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical compound CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- 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 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 238000004898 kneading Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 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
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 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
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明はグラビア印刷或いはフレキソ印刷に於いて、硬化剤を使用しない１液タイプのリキッドインキ組成物、硬化剤を使用する２液タイプのリキッドインキ組成物の両方に関する。 The present invention relates to both a one-component type liquid ink composition that does not use a curing agent and a two-component type liquid ink composition that uses a curing agent in gravure printing or flexographic printing.
主に軟包装材の製造に使用されるラミネート用リキッドインキは、樹脂結着成分として主にウレタン樹脂もしくはウレタンウレア樹脂を主成分として使用している。さらに近年では、印刷時の作業衛生性と包装材料の有害性の両面から、トルエン等の芳香族溶剤やメチルエチルケトン等のケトン系溶剤の使用が制限されつつある。この脱トルエン型のリキッドインキには、印刷適性の観点から、溶剤として芳香族、ケトン系溶剤の代わりに酢酸エチルや酢酸プロピルなどの酢酸エステル類、イソプロピルアルコールやノルマルプロピルアルコール等のアルコール系溶剤又はそれらの混合溶剤が使用される傾向にある。
しかし、このような芳香族溶剤、ケトン系溶剤を使用しないリキッドインキであっても
、大気中への揮発性有機化学物質（ＶＯＣ）の放出は免れない。そこで、ＶＯＣ放出量の
低減のために、水を有機溶剤と併用することが有用であり、かつ水の併用はインキの転移
性向上にも有用である。物性の向上を図るためにイソシアネート硬化剤を添加すること（
２液タイプ）があるが、粘度安定性が劣る傾向にある。特に水が入ると悪くなりやすい傾
向にある。
Liquid inks for laminating, which are mainly used in the production of flexible packaging materials, mainly use urethane resin or urethane urea resin as a main component as a resin binding component. Further, in recent years, the use of aromatic solvents such as toluene and ketone solvents such as methyl ethyl ketone have been restricted from the viewpoints of both work hygiene during printing and harmfulness of packaging materials. From the viewpoint of printability, this detoluene type liquid ink contains aromatic solvents, acetate esters such as ethyl acetate and propyl acetate instead of ketone solvents, alcohol solvents such as isopropyl alcohol and normal propyl alcohol, or alcohol solvents such as normal propyl alcohol. These mixed solvents tend to be used.
However, even with liquid inks that do not use such aromatic solvents and ketone solvents, the release of volatile organic chemical substances (VOCs) into the atmosphere is unavoidable. Therefore, in order to reduce the amount of VOC emissions, it is useful to use water in combination with an organic solvent, and the combined use of water is also useful in improving the transferability of ink. Add an isocyanate curing agent to improve physical properties (
There is a two-component type), but the viscosity stability tends to be inferior. Especially when water gets in, it tends to get worse.
その実例を挙げれば、安定化剤としスチレン無水マレイン酸をポリウレタン樹脂溶液に含有させ経時安定性に優れる印刷インキ用バインダーが開示されている（例えば、特許文献１参照）。しかしながらスチレン無水マレイン酸を添加した場合、硬化剤を添加する２液タイプでは粘度安定性は良好であるが、硬化剤を添加しない１液タイプの場合、粘度安定性は十分であるとは言えない。１液タイプ、２液タイプのどちらの場合であっても、粘度安定性が十分良好である事が望まれる。
また、特許文献２には、グリコールエーテル系有機溶剤と水を含むグラビアインキが開示されているが、これでは特に２液使用時の粘度安定性が十分であるとはいえない。
To give an example thereof, a binder for printing ink, which contains styrene maleic anhydride as a stabilizer in a polyurethane resin solution and has excellent stability over time, is disclosed (see, for example, Patent Document 1). However, when styrene maleic anhydride is added, the two-component type to which a curing agent is added has good viscosity stability, but the one-component type to which no curing agent is added cannot be said to have sufficient viscosity stability. .. In either case of the one-component type or the two-component type, it is desired that the viscosity stability is sufficiently good.
Further, Patent Document 2 discloses a gravure ink containing a glycol ether-based organic solvent and water, but this does not mean that the viscosity stability is particularly sufficient when the two liquids are used.
本発明の課題は、グラビア印刷或いはフレキソ印刷に於いて、カスレ試験、版カブリ試験等の印刷適性、ラミネート強度、耐レトルト性等の基本性能を保持しつつ、硬化剤を使用しない１液タイプ、硬化剤を使用する２液タイプのいずれにおいても粘度安定性に優れるリキッドインキ組成物を提供することにある。また、該リキッドインキ組成物を印刷してなる印刷物、また該リキッドインキを印刷してなる印刷層を有するラミネート積層体を提供することにある。 An object of the present invention is a one-component type that does not use a curing agent in gravure printing or flexographic printing, while maintaining basic performance such as printability such as blur test and plate fog test, laminate strength, and retort resistance. An object of the present invention is to provide a liquid ink composition having excellent viscosity stability in any of the two-component types using a curing agent. Another object of the present invention is to provide a printed matter obtained by printing the liquid ink composition, and a laminated laminate having a printed layer obtained by printing the liquid ink.
本発明は、バインダー樹脂、有機溶剤に粘度安定剤を添加する事で、グラビア印刷或いはフレキソ印刷に於いて、カスレ試験、版カブリ試験等の印刷適性、ラミネート強度、耐レトルト性等の基本性能を保持しつつ、硬化剤を使用しない１液タイプ、硬化剤を使用する２液タイプのいずれにおいても粘度安定性に優れるリキッドインキ組成物を提供することを見出し、発明を完成させた。 The present invention provides basic performance such as printability, laminate strength, and retort resistance in gravure printing or flexographic printing by adding a viscosity stabilizer to a binder resin and an organic solvent, such as a blur test and a plate fog test. We have found that we can provide a liquid ink composition with excellent viscosity stability in both the one-component type that does not use a curing agent and the two-component type that uses a curing agent while retaining the ink, and completed the invention.
すなわち本発明は、第一に、バインダー樹脂（Ａ）、有機溶剤（Ｂ）、及びインキ組成物全量の０．０００１〜１．０質量％の酸無水物（Ｃ）含有することを特徴とするリキッドインキに関する。 That is, the present invention is first characterized by containing the binder resin (A), the organic solvent (B), and the acid anhydride (C) in an amount of 0.0001 to 1.0% by mass of the total amount of the ink composition. Regarding liquid ink.
また、本発明は、前記バインダー樹脂（Ａ）が、ポリウレタン樹脂及び／又はポリウレタンポリウレア樹脂であるリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the binder resin (A) is a polyurethane resin and / or a polyurethane polyurea resin.
また、本発明は、リキッドインキ組成物中に水を１０質量％未満含有するリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition containing less than 10% by mass of water in the liquid ink composition.
また、本発明は、バインダー樹脂（Ａ）が更に、塩化ビニル−酢酸ビニル共重合樹脂を含有するリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the binder resin (A) further contains a vinyl chloride-vinyl acetate copolymer resin.
また、本発明は、更に、着色剤（Ｄ）を含有するリキッドインキ組成物に関する。 The present invention further relates to a liquid ink composition containing a colorant (D).
また、本発明は、前記ポリウレタン樹脂及び／又はポリウレタンウレア樹脂が、アミノ基を有するリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the polyurethane resin and / or the polyurethane urea resin has an amino group.
また、本発明は、前記ポリウレタン樹脂及び／又はポリウレタンウレア樹脂の固形分換算のアミン価が１０．０ｍｇＫＯＨ／ｇ以下であるリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the amine value of the polyurethane resin and / or the polyurethane urea resin in terms of solid content is 10.0 mgKOH / g or less.
また、本発明は、前記有機溶剤（Ｂ）が、芳香族有機溶剤及び／又はケトン系溶剤を含まないリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the organic solvent (B) does not contain an aromatic organic solvent and / or a ketone solvent.
また、本発明は、前記酸無水物（Ｃ）の数平均分子量が１０００以下であるリキッドインキ組成物に関する。 The present invention also relates to a liquid ink composition in which the number average molecular weight of the acid anhydride (C) is 1000 or less.
また、本発明は、該リキッドインキ組成物を印刷してなる印刷物に関する。 The present invention also relates to a printed matter obtained by printing the liquid ink composition.
また、本発明は、該リキッドインキ組成物を印刷してなる印刷層を有するラミネート積層体に関する。 The present invention also relates to a laminated laminate having a printing layer obtained by printing the liquid ink composition.
本発明により、グラビア印刷或いはフレキソ印刷に於いて、カスレ試験、版カブリ試験等の印刷適性、ラミネート強度、耐レトルト性等の基本性能を保持しつつ、硬化剤を使用しない１液タイプ、硬化剤を使用する２液タイプのいずれにおいても粘度安定性に優れるリキッドインキ組成物が得られる。 According to the present invention, in gravure printing or flexographic printing, a one-component type that does not use a curing agent, a curing agent, while maintaining basic performance such as printability such as blur test and plate fog test, laminate strength, and retort resistance. A liquid ink composition having excellent viscosity stability can be obtained in any of the two-component types using.
本発明は、バインダー樹脂（Ａ）、有機溶剤（Ｂ）、及びインキ組成物全量の０．０００１〜１．０質量％の酸無水物（Ｃ）を含有することを特徴とするリキッドインキ組成物を提供する。 The present invention is a liquid ink composition containing a binder resin (A), an organic solvent (B), and an acid anhydride (C) of 0.0001 to 1.0% by mass of the total amount of the ink composition. I will provide a.
本発明のリキッドインキ組成物に必要に応じて併用されるバインダー樹脂（Ａ）の例としては例えば、前記ポリウレタン樹脂、ポリウレタンウレア樹脂、塩素化ポリプロピレン樹脂、エチレン−酢酸ビニル共重合体樹脂、酢酸ビニル樹脂、ポリアミド樹脂、アクリル樹脂、ポリエステル樹脂、アルキッド樹脂、ポリ塩化ビニル樹脂、ロジン系樹脂、ロジン変性マレイン酸樹脂、ケトン樹脂、環化ゴム、塩化ゴム、ブチラール、石油樹脂などを挙げることができる。併用樹脂は、単独で、または２種以上を混合して用いることができる。併用樹脂の含有量は、インキ組成物の総質量に対して固形分換算で１〜５０質量％の範囲であり、更に好ましくは２〜４０質量％である。中でもポリウレタン樹脂、ポリウレタンポリウレア樹脂が好ましく、各々単独で使用しても２種組み合わせ使用してもよい。
本発明のリキッドインキ組成物におけるポリウレタン樹脂及び／又はポリウレタンポリウレア樹脂の含有量は、例えば、グラビア印刷の場合、グラビアインキの被印刷体への接着性を十分にする観点からインキの総質量に対して固形分換算にて５質量％以上、適度なインキ粘度やインキ製造時・印刷時の作業効率の観点から２５質量％以下が好ましく、フレキソ印刷の場合、フレキソインキの総質量に対して固形分換算にて５質量％以上、３０質量％以下であることが好ましい。
Examples of the binder resin (A) used in the liquid ink composition of the present invention as needed include the polyurethane resin, polyurethane urea resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, and vinyl acetate. Examples thereof include resins, polyamide resins, acrylic resins, polyester resins, alkyd resins, polyvinyl chloride resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, rubber chlorides, butyral, and petroleum resins. The combined resin can be used alone or in combination of two or more. The content of the combined resin is in the range of 1 to 50% by mass, more preferably 2 to 40% by mass, in terms of solid content with respect to the total mass of the ink composition. Of these, polyurethane resin and polyurethane polyurea resin are preferable, and each may be used alone or in combination of two.
The content of the polyurethane resin and / or the polyurethane polyurea resin in the liquid ink composition of the present invention is, for example, in the case of gravure printing, with respect to the total mass of the ink from the viewpoint of sufficiently adhering the gravure ink to the printed material. In terms of solid content, 5% by mass or more is preferable, and 25% by mass or less is preferable from the viewpoint of appropriate ink viscosity and work efficiency during ink production / printing. In the case of flexographic printing, the solid content is based on the total mass of flexo ink. In terms of conversion, it is preferably 5% by mass or more and 30% by mass or less.
本発明のリキッドインキ組成物に用いるポリウレタン樹脂、並びにポリウレタンポリウレア樹脂の数平均分子量は、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、ポリウレタンポリウレア樹脂の数平均分子量が１５，０００未満の場合には、得られるインキの耐ブロッキング性、ラミネート強度や耐薬品性などが低くなる傾向があり、１００，０００を超える場合には、得られるインキの粘度が高くなり、所定の印刷濃度が得られない傾向がある。 The number average molecular weight of the polyurethane resin and the polyurethane polyurea resin used in the liquid ink composition of the present invention is preferably in the range of 15,000 to 100,000. When the number average molecular weight of the polyurethane resin or polyurethane polyurea resin is less than 15,000, the blocking resistance, laminate strength, chemical resistance, etc. of the obtained ink tend to be low, and when it exceeds 100,000. , The viscosity of the obtained ink tends to be high, and a predetermined print density tends not to be obtained.
本発明のリキッドインキ組成物で使用するポリウレタン樹脂及び／又はポリウレタンウレア樹脂は、その反応原料として、ポリエステルポリオール及び／又はポリエーテルポリオールを用いる事が好ましい。前記ポリエステルポリオールの数平均分子量が３０００〜７０００ものであることが好ましい。 The polyurethane resin and / or polyurethane urea resin used in the liquid ink composition of the present invention preferably uses a polyester polyol and / or a polyether polyol as a reaction raw material thereof. The number average molecular weight of the polyester polyol is preferably 3000 to 7000.
前記ポリエステルポリオールの数平均分子量が３０００より小さいと、ポリウレタン樹脂及び／又はポリウレタンウレア樹脂の皮膜が硬くなる傾向にありポリエステルフィルムへの接着性が低下し易い。数平均分子量が７０００より大きい場合、ポリウレタン樹脂の皮膜が脆弱になる傾向にありインキ皮膜の耐ブロッキング性が低下し易い。一方で、ポリエーテルポリオールはポリウレタン樹脂１００質量部に対して１〜５０質量部あることが好ましく、ポリエーテルポリオールが１質量部未満であると、該ポリウレタン樹脂のケトン、エステル、アルコール系溶剤への溶解性が低下するのに加え、特に高機能バリアーフィルム上での密着性が低下する傾向となる。またインキ皮膜の該溶剤への再溶解性が低下し、印刷物の調子再現性が低下する傾向となる。また５０質量部を超えると、インキ皮膜が過剰に柔らかくなり、耐ブロッキングが劣る傾向と成り易い。 When the number average molecular weight of the polyester polyol is less than 3000, the film of the polyurethane resin and / or the polyurethane urea resin tends to be hard, and the adhesiveness to the polyester film tends to decrease. When the number average molecular weight is larger than 7,000, the polyurethane resin film tends to be fragile, and the blocking resistance of the ink film tends to decrease. On the other hand, the amount of the polyether polyol is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyurethane resin, and when the amount of the polyether polyol is less than 1 part by mass, the polyurethane resin is added to the ketone, ester and alcohol solvent. In addition to the decrease in solubility, the adhesion on the high-performance barrier film tends to decrease. Further, the resolubility of the ink film in the solvent is lowered, and the tone reproducibility of the printed matter tends to be lowered. On the other hand, if it exceeds 50 parts by mass, the ink film becomes excessively soft, and the blocking resistance tends to be inferior.
なお、前記ポリエステルポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。 The number average molecular weight of the polyester polyol is a value measured under the following conditions by a gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−５５０」
(Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
前記ポリエステルポリオールとしては、例えば、水酸基を２個以上有する化合物と多塩基酸とを公知のエステル化反応により得られるものを用いることができる。
前記水酸基を２個以上有する化合物は鎖伸長剤として用いるものであり、例えば、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール等のグリコール；２−メチル−１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，２−プロパンジオール、２−メチル−１，３−プロパンジオール、ネオペンチルグリコール、２−イソプロピル−１，４−ブタンジオール、２，４−ジメチル−１，５−ペンタンジオール２，４−ジエチル−１，５−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２−エチル−１，６−ヘキサンジオール、３，５−ヘプタンジオール、２−メチル−１，８−オクタンジオール等の分岐構造を有するグリコール；トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール、サッカロース、メチレングリコール、グリセリン、ソルビトール等の脂肪族ポリオール；ビスフェノールＡ、４，４’−ジヒドロキシジフェニル、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルホン、水素添加ビスフェノールＡ、ハイドロキノン等の芳香族ポリオールなどの数平均分子量が５０〜４００の範囲の化合物を用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。
前記多塩基酸としては、例えば、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、無水マレイン酸、フマル酸、１，３−シクロペンタンジカルボン酸、１，４−シクロヘキサンジカルボン酸、フタル酸、これらの酸の無水物等を用いることができる。これらの多塩基酸は単独で用いても２種以上を併用してもよい。
As the polyester polyol, for example, a compound obtained by a known esterification reaction of a compound having two or more hydroxyl groups and a polybasic acid can be used.
The compound having two or more hydroxyl groups is used as a chain extender, and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6. -Glynes such as hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol , 3-Methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 2-Propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1 , 5-Pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptandiol, 2-methyl-1,8-octanediol, etc. Glycols: Trimethylol propane, trimethylol ethane, pentaerythritol, saccharose, methylene glycol, glycerin, sorbitol and other aliphatic polyols; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 Compounds having a number average molecular weight in the range of 50 to 400, such as'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, and aromatic polyols such as hydroquinone, can be used. These chain extenders may be used alone or in combination of two or more.
Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and phthalic acid. Acids, anhydrides of these acids and the like can be used. These polybasic acids may be used alone or in combination of two or more.
また、前記ポリエーテルポリオールは、その数平均分子量が１００〜４０００のものであることが好ましい。詳細は後述するが、ポリエーテルポリオールとしては、酸化エチレン、酸化プロピレン、テトラヒドロフランなどの重合体または共重合体のポリエーテルポリオール類が挙げられる。具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなど公知汎用のものでよく、中ではポリエチレングリコールが好ましい。ポリエステルポリオール及び／又はポリエーテルポリオールを上記の範囲で含有することにより、特に基材フィルム上での密着性が大幅に向上し、結果として耐ブロッキング性、ラミネート強度が優れるようになる。 Further, the polyether polyol preferably has a number average molecular weight of 100 to 4000. Details will be described later, but examples of the polyether polyols include polyether polyols of polymers such as ethylene oxide, propylene oxide, and tetrahydrofuran, or copolymers. Specifically, known general-purpose products such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used, and polyethylene glycol is preferable. By containing the polyester polyol and / or the polyether polyol in the above range, the adhesion particularly on the base film is significantly improved, and as a result, the blocking resistance and the lamination strength are excellent.
同様に、前記ポリエーテルポリオールの数平均分子量が１００より小さいと、ポリウレタン樹脂の皮膜が硬くなる傾向にありポリエステルフィルムへの接着性が低下し易い。数平均分子量が４０００より大きい場合、ポリウレタン樹脂の皮膜が脆弱になる傾向にありインキ皮膜の耐ブロッキング性が低下し易い。尚、ポリエーテルポリオールの数平均分子量は、前記ポリエステルポリオールと同様にゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、同条件で測定した。 Similarly, when the number average molecular weight of the polyether polyol is less than 100, the film of the polyurethane resin tends to be hard, and the adhesiveness to the polyester film tends to decrease. When the number average molecular weight is larger than 4000, the polyurethane resin film tends to be fragile, and the blocking resistance of the ink film tends to decrease. The number average molecular weight of the polyether polyol was measured under the same conditions by the gel permeation chromatography (GPC) method as in the case of the polyester polyol.
本発明のリキッドインキ組成物におけるポリウレタン樹脂に使用されるジイソシアネート化合物としては、ポリウレタン樹脂の製造に一般的に用いられる各種公知の芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートなどが挙げられる。例えば、１，５―ナフチレンジイソシアネート、４，４’―ジフェニルメタンジイソシアネート、４，４’―ジフェニルジメチルメタンジイソシアネート、４，４’―ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３―フェニレンジイソシアネート、１，４―フェニレンジイソシアネート、トリレンジイソシアネート、ブタン―１，４―ジイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、２，２，４―トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサン―１，４―ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジメリールジイソシアネート、イソホロンジイソシアネート（３−イソシアナトメチル−３，５，５−トリメチルシクロヘキシルイソシアネート； ５−イソシアナト-1-(イソシアノメチル)−１，３，３−トリメチルシクロヘキサン;）、ジシクロヘキシルメタン―４，４’―ジイソシアネート、１，３―ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ノルボルナンジイソシアネート、ｍーテトラメチルキシリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ビス−クロロメチル−ジフェニルメタン−ジイソシアネート、２，６−ジイソシアネート−ベンジルクロライドやダイマー酸のカルボキシル基をイソシアネート基に転化したダイマージイソシアネート等があげられる。これらのジイソシアネート化合物は単独で、または２種以上を混合して用いることができる。 Examples of the diisocyanate compound used in the polyurethane resin in the liquid ink composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethanediisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1 , 4-Diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; 5-isocyanato-1- (isocyanomethyl) -1,3 , 3-trimethylcyclohexane;), dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, norbornan diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethanediisocyanate , Tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimer diisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group, and the like. These diisocyanate compounds can be used alone or in admixture of two or more.
本発明のリキッドインキ組成物におけるポリウレタン樹脂に使用される鎖伸長剤としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、ジシクロヘキシルメタン―４，４’―ジアミンなどの他、２―ヒドロキシエチルエチレンジアミン、２―ヒドロキシエチルプロピルジアミン、２―ヒドロキシエチルプロピレンジアミン、ジ―２―ヒドロキシエチルエチレンジアミン、ジ―２―ヒドロキシエチレンジアミン、ジ―２―ヒドロキシエチルプロピレンジアミン、２―ヒドロキシピロピルエチレンジアミン、ジ―２―ヒドロキシピロピルエチレンジアミン、ジ―２―ヒドロキシプロピルエチレンジアミンなど分子内に水酸基を有するアミン類も用いることが出来る。これらの鎖伸長剤は単独で、または２種以上を混合して用いることができる。 Examples of the chain extender used in the polyurethane resin in the liquid ink composition of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like. 2,2-Hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrropyl Amines having a hydroxyl group in the molecule such as ethylenediamine, di-2-hydroxypyropylethylenediamine, and di-2-hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more.
更に、本発明のリキッドインキ組成物に使用されるポリウレタン樹脂及び／又はポリウレタンウレア樹脂のアミン価は、１０．０ｍｇＫＯＨ／ｇ以下であることが好ましい。アミン価が１０．０ｍｇＫＯＨ／ｇを上回ると耐ブロッキング性が劣る傾向と成り易いのに加え、硬化剤添加後の２液安定性が低下する。耐ブロッキング性、２液安定性を良好に保ちつつ、版カブリ性、接着性及び押出しラミネート強度を保持できる観点から１．０〜５．０ｍｇＫＯＨ／ｇの範囲がより好ましく、更に好ましくは１．０〜３．５ｍｇＫＯＨ／ｇの範囲である。 Further, the amine value of the polyurethane resin and / or the polyurethane urea resin used in the liquid ink composition of the present invention is preferably 10.0 mgKOH / g or less. If the amine value exceeds 10.0 mgKOH / g, the blocking resistance tends to be inferior, and the two-component stability after the addition of the curing agent is lowered. The range of 1.0 to 5.0 mgKOH / g is more preferable, and more preferably 1.0, from the viewpoint of maintaining plate fog resistance, adhesiveness, and extrusion laminate strength while maintaining good blocking resistance and two-component stability. It is in the range of ~ 3.5 mgKOH / g.
本発明のリキッドインキ組成物で使用する有機溶剤（Ｂ）としては、各種有機溶剤を使用することができ、例えば、トルエン、キシレン等の芳香族有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、酢酸エチル、酢酸ｎ−プロピル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤、ｎ−プロパノール、イノプロパノール、ｎ−ブタノール、プロピレングリコールモノメチルエーテル等のアルコール系溶剤があげられ、これらを単独または２種以上の混合物で用いることができる。
尚、近年、作業環境の観点から、トルエン、キシレンといった芳香族系溶剤やケトン系溶剤を用いないことがより好ましい。
As the organic solvent (B) used in the liquid ink composition of the present invention, various organic solvents can be used, for example, aromatic organic solvents such as toluene and xylene, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Examples include system solvents, ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, and alcohol solvents such as n-propanol, inopropanol, n-butanol and propylene glycol monomethyl ether. Can be used alone or in admixture of two or more.
In recent years, from the viewpoint of the working environment, it is more preferable not to use an aromatic solvent such as toluene or xylene or a ketone solvent.
更に、本発明のリキッドインキ組成物では、酸無水物（Ｃ）をインキ組成物全量の０．０００１〜１．０質量％含有する事を必須とする。前記バインダー樹脂（Ａ）、有機溶剤（Ｂ）、及びインキ組成物全量の０．０００１〜１．０質量％の酸無水物（Ｃ）を含有する構成により、硬化剤を使用しない１液タイプ、硬化剤を使用する２液タイプのいずれにおいても粘度安定性に優れるリキッドインキ組成物が得られる。
前記酸無水物（Ｃ）としては、環式ジカルボン酸の無水物が好ましく、具体的には無水コハク酸、無水マレイン酸、無水フタル酸、ヘキサヒドロ無水フタル酸、無水トリメリット酸等が挙げられる。中でも、無水コハク酸がより好ましい。
前記酸無水物（Ｃ）の添加量は、リキッドインキ組成物全量の０．０００１〜１．０質量％が好ましく、０．００１〜０．５質量％であればより好ましい。０．０００１質量％を下回ると２液の粘度安定性の効果が見られず、また１．０質量％を上回ると経時によるインキ自体の安定性が低下し、カスレ・版カブリ等印刷品質の低下及び耐レトルト性が低下する傾向がみられる。
更に、前記酸無水物（Ｃ）の数平均分子量が１０００以下である事が好ましい。数平均分子量が１０００を上回ると、インキ自体の安定性が低下し、カスレ・版カブリ等印刷品質の低下及び耐レトルト性が低下する傾向がみられる。
Further, in the liquid ink composition of the present invention, it is essential that the acid anhydride (C) is contained in an amount of 0.0001 to 1.0% by mass based on the total amount of the ink composition. A one-component type that does not use a curing agent due to the composition containing the binder resin (A), the organic solvent (B), and the acid anhydride (C) of 0.0001 to 1.0% by mass of the total amount of the ink composition. A liquid ink composition having excellent viscosity stability can be obtained in any of the two-component types using a curing agent.
The acid anhydride (C) is preferably an anhydride of a cyclic dicarboxylic acid, and specific examples thereof include succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride. Of these, succinic anhydride is more preferable.
The amount of the acid anhydride (C) added is preferably 0.0001 to 1.0% by mass, more preferably 0.001 to 0.5% by mass, based on the total amount of the liquid ink composition. If it is less than 0.0001% by mass, the effect of viscosity stability of the two liquids is not seen, and if it exceeds 1.0% by mass, the stability of the ink itself decreases with time, and the printing quality such as blurring and plate fog deteriorates. And the retort resistance tends to decrease.
Further, it is preferable that the number average molecular weight of the acid anhydride (C) is 1000 or less. When the number average molecular weight exceeds 1000, the stability of the ink itself is lowered, the printing quality such as blurring and plate fog is lowered, and the retort resistance tends to be lowered.
本発明のリキッドインキ組成物には、揮発性成分として有機溶剤とともに、インキ組成物中に１０質量％未満の含有量で、水を含有させることが出来る。更に、１〜５質量％の範囲であることが、印刷適性が良好となることから、特に好ましい。
この場合、前記の水は、有機溶剤に添加して、含水の有機溶媒としてもよいし、別途特定量の水を添加してもよい。
The liquid ink composition of the present invention can contain water as a volatile component together with an organic solvent in an ink composition having a content of less than 10% by mass. Further, the range of 1 to 5% by mass is particularly preferable because the printability is good.
In this case, the water may be added to the organic solvent to serve as a water-containing organic solvent, or a specific amount of water may be added separately.
更に、インキ皮膜に耐熱性を求めるためには、ポリウレタンポリウレア樹脂のように尿素結合を有する樹脂が有効である。そして、尿素結合同士が水素結合で結びつくことでインキの粘度が高くなり印刷適性が悪化する傾向がある。そのような現象を防止するため、尿素結合と水素結合で結びついた樹脂の粘度を低下させるべく、水をインキ組成物中に１０質量％未満の含有量で含有させることが好ましい。また、このような水の添加により、使用有機溶剤成分を低減させることも可能である。
更に、水の添加により、インキの乾燥性を制御する機能もあり、特にグラビア印刷では、その特徴であるインキ転移量のすくないグラデーション部をきれいに再現することができる。
Further, in order to obtain heat resistance of the ink film, a resin having a urea bond such as a polyurethane polyurea resin is effective. Then, when the urea bonds are bonded to each other by hydrogen bonds, the viscosity of the ink tends to increase and the printability tends to deteriorate. In order to prevent such a phenomenon, it is preferable to contain water in the ink composition in a content of less than 10% by mass in order to reduce the viscosity of the resin bonded by the urea bond and the hydrogen bond. Further, by adding such water, it is possible to reduce the organic solvent component used.
Further, there is also a function of controlling the drying property of the ink by adding water, and particularly in gravure printing, it is possible to clearly reproduce the gradation portion having a small amount of ink transfer, which is a feature thereof.
更に、本発明のリキッドインキ組成物に、塩化ビニル−酢酸ビニル共重合樹脂を添加することができる。
本発明のリキッドインキ組成物に用いられる、塩化ビニル酢酸ビニル共重合樹脂は、例えば、塩化ビニルと酢酸ビニルを共重合させて得られるものであるが、樹脂中に水酸基を有していてよい。このような水酸基を有する塩化ビニル酢酸ビニル共重合樹脂は、塩化ビニルと酢酸ビニル樹脂を共重合させた後、一部加水分解することにより水酸基を導入したり、あるいは重合時に、塩化ビニル、酢酸ビニル以外の水酸基を有する成分、例えば、メタアクリル酸−２−ヒドロキシルエチル等を、添加して共重合させたりすることにより水酸基を導入することにより得られる。水酸基を有する塩化ビニル酢酸ビニル共重合体樹脂としては、市販品のものを利用することもできる。
水酸基を有する塩化ビニル酢酸ビニル共重合樹脂は、塩化ビニル骨格、酢酸ビニル骨格およびビニルアルコール骨格等の水酸基含有構造の含有比率により樹脂被膜の性質や樹脂溶解挙動が決定される。即ち、塩化ビニルは樹脂被膜の強靭さや硬さを付与し、酢酸ビニルは接着性や柔軟性を付与し、ビニルアルコール等の水酸基は極性溶剤への良好な溶解性を付与する。尚、全樹脂成分中に固形分換算にて０．１〜５．０質量％含有することが好ましい。
Further, a vinyl chloride-vinyl acetate copolymer resin can be added to the liquid ink composition of the present invention.
The vinyl chloride vinyl acetate copolymer resin used in the liquid ink composition of the present invention is obtained by, for example, copolymerizing vinyl chloride and vinyl acetate, but the resin may have a hydroxyl group. A vinyl chloride vinyl acetate copolymer resin having such a hydroxyl group can be introduced with a hydroxyl group by partially hydrolyzing after copolymerizing vinyl chloride and a vinyl acetate resin, or vinyl chloride or vinyl acetate at the time of polymerization. It is obtained by introducing a hydroxyl group by adding and copolymerizing a component having a hydroxyl group other than, for example, -2-hydroxylethyl methacrylic acid. As the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group, a commercially available product can also be used.
In the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group, the properties of the resin film and the resin dissolution behavior are determined by the content ratio of the hydroxyl group-containing structure such as the vinyl chloride skeleton, the vinyl acetate skeleton and the vinyl alcohol skeleton. That is, vinyl chloride imparts toughness and hardness of the resin film, vinyl acetate imparts adhesiveness and flexibility, and hydroxyl groups such as vinyl alcohol impart good solubility in polar solvents. It is preferable that the total resin component contains 0.1 to 5.0% by mass in terms of solid content.
発明のリキッドインキ組成物で用いる着色剤としては、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 Ｎｏ Ｙｅｌｌｏｗ８３を用いることが好ましい。 Examples of the colorant used in the liquid ink composition of the present invention include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like. Organic pigments include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, dictopyrrolopyrrole-based, and isoindoline-based. Pigments can be mentioned. Copper phthalocyanine for indigo ink and C.I. I. It is preferable to use Pigment No Yellow 83.
例えば、ピグメントＣ．Ｉ．ナンバーとして、Ｂｌａｃｋ７、Ｙ１２、Ｙ１３、Ｙ１４、Ｙ１７、Ｙ８３、Ｙ７４、Ｙ−１５４、Ｙ１８０、Ｒ５７：１、Ｒ１２２、Ｒ４８：１、Ｒ４８：２、Ｒ４８：３、Ｒ５３：１、Ｒ１４６、Ｒ−１５０、Ｒ−１６６、Ｒ１７０、Ｒ１８４、Ｒ１８５、Ｖ１９、Ｖ２３、Ｖ３２、Ｏ１３、Ｏ１６、Ｏ３４、Ｇ７、Ｇ３６、Ｂ１５：３、Ｂ１５：４、Ｗ６等が挙げられる。 For example, Pigment C.I. I. As numbers, Black7, Y12, Y13, Y14, Y17, Y83, Y74, Y-154, Y180, R57: 1, R122, R48: 1, R48: 2, R48: 3, R53: 1, R146, R-150. , R-166, R170, R184, R185, V19, V23, V32, O13, O16, O34, G7, G36, B15: 3, B15: 4, W6 and the like.
前記無機顔料としては、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。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種以上を併用して用いることができる。 Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, mica (mica) and the like. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica (mica) for pearl ink from the viewpoint of cost and coloring power. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration. The colorant is preferably contained in an amount sufficient to secure the density and coloring power of the ink, that is, in a ratio of 1 to 50% by weight with respect to the total weight of the ink. In addition, the colorants can be used alone or in combination of two or more.
これらの有機顔料並びに無機顔料は、前記した水分の添加により、インキの乾燥性や印刷特性を向上する効果も有している。 These organic pigments and inorganic pigments also have the effect of improving the drying property and printing characteristics of the ink by adding the above-mentioned water content.
（通常の製造方法）
本発明のリキッドインキ組成物の製造は、例えば、ポリウレタン樹脂に、着色用顔料、体質顔料、溶剤、ヒドロキシカルボン酸及び、必要に応じて、帯電防止剤、ブロッキング防止剤、可塑剤などの添加剤、インキ流動性および分散性を改良するための界面活性剤、あるいはポリウレタン樹脂と相溶性を有する樹脂を、経時で増粘とゲル化が生じない範囲にて併用し、ボールミル、アトライター、サンドミルなどの通常の印刷インキ製造装置を用いて混練することによってなされる。特に、帯電防止剤の添加は、エステル系溶剤、ケトン系溶剤を使用時に発生しやすいヒゲ、雷筋と呼ばれる印刷時の静電気トラブルの抑制に効果的である。
(Normal manufacturing method)
In the production of the liquid ink composition of the present invention, for example, a coloring pigment, an extender pigment, a solvent, a hydroxycarboxylic acid, and, if necessary, an additive such as an antistatic agent, an antiblocking agent, and a plasticizer are added to the polyurethane resin. , A surfactant for improving ink fluidity and dispersibility, or a resin compatible with polyurethane resin is used in combination as long as thickening and gelation do not occur over time, such as ball mills, attritors, and sand mills. It is done by kneading using the usual printing ink manufacturing apparatus of. In particular, the addition of an antistatic agent is effective in suppressing static electricity troubles during printing called whiskers and thunder streaks, which are likely to occur when an ester solvent or a ketone solvent is used.
本発明は、前記したリキッドインキ組成物の印刷によって得られる印刷物、及びリキッドインキを印刷してなる印刷層を有するラミネート積層体をも提供する。 The present invention also provides a printed matter obtained by printing the liquid ink composition described above, and a laminated laminate having a printed layer obtained by printing the liquid ink.
以下に、実施例を用いて本発明を具体的に説明する。尚、実施例中の「部」は質量部を、「％」は質量％を表す。
尚、本発明におけるＧＰＣ（ゲルパーミエーションクロマトグラフィー）による酸無水物の数平均分子量、及びポリウレタン樹脂の重量平均分子量（ポリスチレン換算）の測定は東ソー(株)社製ＨＬＣ８２２０システムを用い以下の条件で行った。
分離カラム：東ソー（株）製ＴＳＫｇｅｌＧＭＨＨＲ−Ｎを４本使用。カラム温度：４０℃。移動層：和光純薬工業（株）製テトラヒドロフラン。流速：１．０ｍｌ／分。試料濃度：０．４質量％。試料注入量：１００マイクロリットル。検出器：示差屈折計。
また、アミン価は、ポリウレタン樹脂１ｇ中に含有するアミノ基を中和するのに必要となる塩酸の当量と同量の水酸化カリウム（ＫＯＨ）のｍｇ数を示すものである。その測定方法としては、試料量Ｐグラム精秤した試料に中性エタノール３０ｍＬを添加・溶解させた後、得られた溶液を０．２ｍｏｌ／Ｌエタノール性塩酸溶液（力価ｆ）で滴定を行う。溶液の色が緑から黄色に変化した時点を終点とみなし、この時の滴定量（ＨｍＬ）を用いて次の（式２）によりアミン価を求めた。
尚、前記試料とは、各合成例で得られるポリウレタン樹脂溶液を指し、固形分質量換算３０％にて算出する。
アミン価＝（Ｈ×ｆ×０．２×５６．１０８）／Ｐ／０．３〔ｍｇＫＯＨ／ｇ〕
Hereinafter, the present invention will be specifically described with reference to Examples. In the examples, "parts" represents parts by mass and "%" represents% by mass.
The number average molecular weight of the acid anhydride and the weight average molecular weight (in terms of polystyrene) of the polyurethane resin by GPC (gel permeation chromatography) in the present invention were measured using the HLC8220 system manufactured by Tosoh Corporation under the following conditions. ..
Separation column: Uses 4 TSKgelGMH HR-N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 0.4% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
The amine value indicates the mg number of potassium hydroxide (KOH), which is the same amount as the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of the polyurethane resin. As a measuring method, after adding and dissolving 30 mL of neutral ethanol to a sample in which the sample amount is P-grams precisely weighed, the obtained solution is titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer f). .. The time when the color of the solution changed from green to yellow was regarded as the end point, and the amine titer was determined by the following (Equation 2) using the titration amount (HmL) at this time.
The sample refers to the polyurethane resin solution obtained in each synthesis example, and is calculated in terms of solid content mass of 30%.
Amine value = (H × f × 0.2 × 56.108) /P/0.3 [mgKOH / g]
（ポリウレタン樹脂溶液Ｐの調製）
攪拌機、温度計、環流冷却器および窒素ガス導入管を備えた４つ口フラスコに、エチレングリコールとネオペンチルグリコールの混合物（モル比＝１／１）とアジピン酸とを反応させて得た数平均分子量１，８００のポリエステルジオール６０５．９部およびイソホロンジイソシアネート９４部を仕込み、窒素気流下に９０℃で１０時間反応させ、遊離イソシアネート価１．０２重量％のプレポリマーを製造した後、これに酢酸エチル３００部を加えてウレタンプレポリマー（Ｂ２）を得た。
続いて、イソホロンジアミン１８．１部、酢酸エチル８７３部およびＩＰＡ５０３部からなる混合物に、前記ウレタンプレポリマー溶液を添加し、４５℃で８時間攪拌反応させて、樹脂固形分濃度３０．５質量％、重量平均分子量５８，０００、アミン価５．３（ｍｇＫＯＨ／ｇ）のポリウレタン樹脂溶液（Ｐ）を得た。
(Preparation of polyurethane resin solution P)
Number average obtained by reacting a mixture of ethylene glycol and neopentyl glycol (molar ratio = 1/1) with adipic acid in a four-necked flask equipped with a stirrer, thermometer, recirculation cooler and nitrogen gas introduction tube. 605.9 parts of polyester diol having a molecular weight of 1,800 and 94 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a prepolymer having a free isocyanate value of 1.02% by weight. 300 parts of ethyl was added to obtain a urethane prepolymer (B2).
Subsequently, the urethane prepolymer solution was added to a mixture consisting of 18.1 parts of isophoronediamine, 873 parts of ethyl acetate and 503 parts of IPA, and the mixture was stirred and reacted at 45 ° C. for 8 hours to have a resin solid content concentration of 30.5% by mass. , A polyurethane resin solution (P) having a weight average molecular weight of 58,000 and an amine value of 5.3 (mgKOH / g) was obtained.
（塩化ビニル酢酸ビニル共重合樹脂溶液Vの調整）
ポリウレタン樹脂と併用して用いる水酸基を有する塩化ビニル酢酸ビニル共重合樹脂（樹脂モノマー組成が質量％で塩化ビニル／酢酸ビニル／ビニルアルコール＝９２／３／５、水酸基価（ｍｇＫＯＨ）＝６４）を酢酸ｎ−プロピルで１５％溶液とし、これを塩酢ビ樹脂溶液（Ｖ）した。
(Adjustment of vinyl chloride vinyl acetate copolymer resin solution V)
Vinyl chloride vinyl acetate copolymer resin having a hydroxyl group used in combination with a polyurethane resin (vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mgKOH) = 64 with a resin monomer composition of mass%) is acetic acid. A 15% solution was made with n-propyl, and this was made into a vinyl chloride resin solution (V).
（実施例１）
ポリウレタン樹脂溶液Ｐ（固形分３０％）を２５部、塩酢ビ樹脂溶液Ｖ（固形分１５％）１０部、酸化チタン顔料テイカ（株）製ＪＲ−７８０ ４５部、イソプロピルアルコール１０部、酢酸エチル２７部からなる混合物をダイノーミル（ウィリー・エ・バッコーフェノン社製）を用いて混練し、得られた白色練肉ベースインキ（Ｗ）に更に水４部と無水コハク酸（ジヒドロ−２，５-フランジオン、数平均分子量１００．０７）を０．０００１部を添加し、本発明のリキッド白インキを作製した。
(Example 1)
25 parts of polyurethane resin solution P (solid content 30%), 10 parts of salt and vinegar resin solution V (solid content 15%), 45 parts of JR-780 manufactured by Titanium Oxide Pigment Teika Co., Ltd., 10 parts of isopropyl alcohol, ethyl acetate A mixture consisting of 27 parts was kneaded using a dynomill (manufactured by Willy et Bacco Phenon), and the obtained white kneaded meat base ink (W) was further mixed with 4 parts of water and succinic anhydride (dihydro-2,5). -Frangion, number average molecular weight 100.07) was added in 0.0001 parts to prepare the liquid white ink of the present invention.
（実施例２〜１０）
実施例１の無水コハク酸の代わりに、無水マレイン酸の他、各種酸無水物を表１に示す量で添加し、実施例と同様の手順にて白色練肉ベースインキ（Ｗ）を作製した。
尚、各酸無水物の数平均分子量は、無水マレイン酸（９８．０６）、ヘキサヒドロ無水フタル酸（１９６．２）、無水フタル酸（１４８．１２）、無水トリメリット酸（１９２．１３）である。
また、実施例１０は「水」を無添加とした。
（比較例１〜４）
比較例１、２については、酸無水物（Ｃ）の代わりに、スチレン・マレイン酸樹脂（X−２２８ 固形分４０％ 星光ＰＭＣ（株）製）を、（表２）の配合に従って添加した。比較例３については、酸無水物（Ｃ）を無添加とした。
比較例４については、無水タイプでないコハク酸を使用した。
(Examples 2 to 10)
Instead of succinic anhydride of Example 1, maleic anhydride and various acid anhydrides were added in the amounts shown in Table 1 to prepare a white kneaded meat base ink (W) by the same procedure as in Example. ..
The number average molecular weight of each acid anhydride is maleic anhydride (98.06), hexahydrophthalic anhydride (196.2), phthalic anhydride (148.12), and trimellitic anhydride (192.13).
Further, in Example 10, "water" was not added.
(Comparative Examples 1 to 4)
For Comparative Examples 1 and 2, styrene-maleic acid resin (X-228 solid content 40%, manufactured by Seiko PMC Corporation) was added instead of the acid anhydride (C) according to the formulation shown in (Table 2). In Comparative Example 3, the acid anhydride (C) was not added.
For Comparative Example 4, non-anhydrous type succinic acid was used.
上記で得られた実施例１〜１０及び比較例１〜４のリキッド白インキについて、以下の評価を実施した。 The following evaluations were carried out on the liquid white inks of Examples 1 to 10 and Comparative Examples 1 to 4 obtained above.
（粘度測定）
リキッド白インキを離合社製ザーンカップＮｏ．４を用いてインキ製造直後に液温２５℃にて粘度を測定した上で、下記１液での粘度安定性、イソシアネート硬化剤を用いた２液安定性を各々評価した。
(Viscosity measurement)
Liquid white ink is used for Zahn Cup No. Immediately after the production of the ink using No. 4, the viscosity was measured at a liquid temperature of 25 ° C., and then the viscosity stability of the following one liquid and the stability of the two liquids using the isocyanate curing agent were evaluated.
（粘度安定性）
リキッド白インキを各々ガラス瓶に採取し、５０℃で２４時間保存を行った。その後、２５℃にて粘度を測定して１液での保存前との粘度変化を評価した。評価基準は以下の通りとした。
（評価）
５：粘度変化が無い 粘度変化が ２秒未満
４：粘度変化が少し 粘度変化が ２秒以上５秒未満
３：粘度変化がやや多い 粘度変化が ５秒以上１０秒未満
２：粘度変化が多い 粘度変化が１０秒以上１５秒未満
１：粘度変化が非常に多い 粘度変化が１５秒以上
(Viscosity stability)
Each liquid white ink was collected in a glass bottle and stored at 50 ° C. for 24 hours. Then, the viscosity was measured at 25 ° C. to evaluate the change in viscosity with that before storage in one liquid. The evaluation criteria are as follows.
(Evaluation)
5: No change in viscosity Viscosity change is less than 2 seconds 4: Viscosity change is slight Viscosity change is 2 seconds or more and less than 5 seconds 3: Viscosity change is slightly more Viscosity change is 5 seconds or more and less than 10 seconds 2: Viscosity change is large Change is 10 seconds or more and less than 15 seconds 1: Viscosity change is very large Viscosity change is 15 seconds or more
（２液安定性）
リキッド白インキをガラス瓶に採取し、其々インキ１００質量％にＣＶＬ ＮＯ．１０ハードナー（イソシアネート硬化剤：ＤＩＣ製）を４質量％添加し、４０℃で２４時間保存した後、粘度を測定して保存前との粘度変化を評価した。評価基準は以下の通りとした。
（評価）
５：粘度変化が無い 粘度変化が ２秒未満
４：粘度変化が少し 粘度変化が ２秒以上５秒未満
３：粘度変化がやや多い 粘度変化が ５秒以上１０秒未満
２：粘度変化が多い 粘度変化が１０秒以上１５秒未満
１：粘度変化が非常に多い 粘度変化が１５秒以上
(Two-component stability)
Liquid white ink was collected in a glass bottle, and CVL NO. After adding 4% by mass of 10 hardener (isocyanate curing agent: manufactured by DIC) and storing at 40 ° C. for 24 hours, the viscosity was measured to evaluate the change in viscosity from that before storage. The evaluation criteria are as follows.
(Evaluation)
5: No change in viscosity Viscosity change is less than 2 seconds 4: Viscosity change is slight Viscosity change is 2 seconds or more and less than 5 seconds 3: Viscosity change is slightly more Viscosity change is 5 seconds or more and less than 10 seconds 2: Viscosity change is large Change is 10 seconds or more and less than 15 seconds 1: Viscosity change is very large Viscosity change is 15 seconds or more
（印刷適性試験：カスレ試験）
酢酸エチル／イソプロピルアルコール＝５０／５０の混合有機溶剤でインキを希釈し、離合社製ザーンカップＮＯ．３で１５秒になるように希釈した。それを版深度２５μｍを有するグラビア版を取り付けたグラビア印刷機（ＤＩＣエンジニアリング株式会社製）を用いて、片面にコロナ処理を施した二軸延伸ポリエステルフィルム（東洋紡績株式会社製 Ｅ−５１００ 厚さ１２μｍ）の処理面に印刷を行った。そして印刷物の印刷部分へのインキの転移度（カスレ度）を評価した。カスレ試験は、グラビア版の円周６００ｍｍφで３００ｍ／分の印刷速度での評価を行った。評価基準は以下の通りとした。
（評価）
５：カスレ無し
４：カスレがごく僅かに確認できる
３：カスレが僅かに確認できるが実用範囲である
２：カスレが発生している
１：カスレが著しく発生している
(Printability test: Cassoulet test)
The ink was diluted with a mixed organic solvent of ethyl acetate / isopropyl alcohol = 50/50, and Zahn Cup NO. Dilute with 3 for 15 seconds. A biaxially stretched polyester film (E-5100, manufactured by Toyo Spinning Co., Ltd.) with corona treatment on one side using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 25 μm. ) Was printed. Then, the degree of ink transfer (cassoulet degree) to the printed portion of the printed matter was evaluated. The blur test was evaluated at a printing speed of 300 m / min with a circumference of 600 mmφ of the gravure plate. The evaluation criteria are as follows.
(Evaluation)
5: No blurring 4: Very slight blurring can be confirmed 3: Slight blurring can be confirmed but within the practical range 2: Cassoulet has occurred 1: Cassoulet has occurred remarkably
（印刷適性試験：版かぶり試験）
上記カスレ試験の条件で印刷した時の印刷物の中で、非印刷部の汚れ具合（版かぶり度）を評価した。
（評価）
５：印刷汚れ無し
４：印刷汚れがごく僅かに確認できる
３：印刷汚れが僅かに確認できるが実用範囲である
２：印刷汚れが発生している
１：印刷汚れが著しく発生している
(Printability test: Plate fog test)
The degree of stain (plate fog degree) of the non-printed portion was evaluated in the printed matter when printed under the above-mentioned blur test conditions.
(Evaluation)
5: No print stains 4: Very slight print stains can be confirmed 3: Print stains can be slightly confirmed but within the practical range 2: Print stains have occurred 1: Print stains have occurred significantly
（ラミネート強度）
印刷物にウレタン系のドライラミネート接着剤ディックドライＬＸ−７０３ＶＬ／ＫＲ−９０（ＤＩＣ製）にてドライラミネート機（ＤＩＣエンジニアリング製）によって無延伸ポリプロピレンフィルム（以下、Ｒ−ＣＰＰ：東レ合成フィルム社製 ＺＫ−７５ ５０μｍ）を積層し、４０℃で５日間エージング施し、ラミネート物を得た後、１５ｍｍ幅に切り出し引っ張り速度３００ｍｍ／分で９０度剥離試験（レトルト処理前のラミネート強度の測定）を行った。
さらに、得られたラミネート物を１２０ｍｍ×１２０ｍｍの大きさのパウチに製袋し、内容物として、食酢、サラダ油、ミートソースを重量比で１：１：１に配合した疑似食品７０ｇを充填密封した。作成したパウチを１２０℃、３０分間の蒸気レトルト殺菌処理をした後、上記と同様に９０度剥離試験（レトルト処理後のラミネート強度の測定）を行った。
（評価）
○：ラミネート強度が５００（ｇ／１５ｍｍ）以上であり強度充分。
△：ラミネート強度が３００以上〜５００（ｇ／１５ｍｍ）未満でありやや強度不足である。
×：ラミネート強度が３００（ｇ／１５ｍｍ）未満であり強度不充分。
(Laminate strength)
Urethane-based dry laminating adhesive for printed matter Dick dry LX-703VL / KR-90 (manufactured by DIC) with a dry laminating machine (manufactured by DIC Engineering) Non-stretched polypropylene film (hereinafter, R-CPP: manufactured by Toray Synthetic Film Co., Ltd. ZK -75 50 μm) was laminated and aged at 40 ° C. for 5 days to obtain a laminate, which was then cut into a width of 15 mm and subjected to a 90 degree peeling test (measurement of laminate strength before retort treatment) at a pulling speed of 300 mm / min. ..
Further, the obtained laminate was made into a bag in a pouch having a size of 120 mm × 120 mm, and 70 g of a simulated food containing vinegar, salad oil and minced meat sauce in a weight ratio of 1: 1: 1 was filled and sealed as the contents. The prepared pouch was subjected to steam retort sterilization treatment at 120 ° C. for 30 minutes, and then a 90-degree peeling test (measurement of laminate strength after retort treatment) was performed in the same manner as described above.
(Evaluation)
◯: Laminate strength is 500 (g / 15 mm) or more, and the strength is sufficient.
Δ: The laminate strength is 300 or more and less than 500 (g / 15 mm), and the strength is slightly insufficient.
X: The laminate strength is less than 300 (g / 15 mm) and the strength is insufficient.
（耐レトルト性）
上記印刷物をドライラミネート加工後、ラミネート物を製袋し、内容物として、水／サラダ油の混合物を入れ、密封後、１２５℃、３０分間加熱した後、ラミ浮きの有無を外観により目視判定した。
（評価）
○：全くラミ浮きがない。
△：ごく一部がデラミネーションしているか、またはブリスターがわずかに生じた。
×：全面デラミネーションが生じた。
(Retort resistance)
After the printed matter was dry-laminated, the laminate was made into a bag, a mixture of water / salad oil was added as the content, and after sealing, the printed matter was heated at 125 ° C. for 30 minutes, and then the presence or absence of lami floating was visually determined by appearance.
(Evaluation)
◯: There is no Lami float at all.
Δ: Only a small part was delaminated, or blisters were slightly generated.
X: Full-scale delamination occurred.
以上の結果から、本発明のリキッドインキ組成物は、カスレ試験、版カブリ試験等の印刷適性、ラミネート強度、耐レトルト性等の基本性能を保持しつつ、硬化剤を使用しない１液タイプ、硬化剤を使用する２液タイプのいずれにおいても粘度安定性に優れる。 Based on the above results, the liquid ink composition of the present invention is a one-component type that does not use a curing agent and cures while maintaining basic performance such as printability, laminate strength, and retort resistance such as blur test and plate fog test. Excellent viscosity stability in both two-component types that use agents.
本発明のリキッドインキ組成物は、グラビア印刷或いはフレキソ印刷に於いて、環境面、衛生面に配慮した脱トルエン型低粘度液体インキであり、食品包材・サニタリー・コスメ・電子部品等工業製品向け軟包装用途に幅広く展開され得る。 The liquid ink composition of the present invention is a toluene-free low-viscosity liquid ink in consideration of the environment and hygiene in gravure printing or flexographic printing, and is intended for industrial products such as food packaging materials, sanitary products, cosmetics, and electronic parts. Can be widely deployed in flexible packaging applications.
Claims (10)
前記着色剤（Ｄ）は有機顔料、染料、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、シリカ及びベンガラから選択されることを特徴とするリキッドインキ組成物。 Binder resin (A), the contain an organic solvent (B), 0.0001 to 1.0 wt% of the acid anhydride Lee Nki total composition (C), and colorant (D),
The liquid ink composition, wherein the colorant (D) is selected from organic pigments, dyes, carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica and red iron oxide.
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| JP6871084B2 true JP6871084B2 (en) | 2021-05-12 |
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| JPH07145337A (en) * | 1993-11-25 | 1995-06-06 | Matsumoto Seiyaku Kogyo Kk | Printing ink composition |
| JP2002020670A (en) * | 2000-07-07 | 2002-01-23 | Mitsui Chemicals Inc | Solvent for printing ink |
| JP2003206431A (en) * | 2002-01-16 | 2003-07-22 | Hitachi Kasei Polymer Co Ltd | Binder for printing ink and printing ink |
| JP4200691B2 (en) * | 2002-05-31 | 2008-12-24 | Ｄｉｃ株式会社 | High brightness printing ink composition for laminated cans |
| JP4424446B1 (en) * | 2009-03-25 | 2010-03-03 | 東洋インキ製造株式会社 | Printing ink composition for laminating |
| US9873805B2 (en) * | 2015-06-10 | 2018-01-23 | Flint Group North America Corporation | Solvent-based flexible packaging ink composition for high temperature and pressure |
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