JP5130553B1 - Polyurethane resin composition for printing ink binder - Google Patents
Polyurethane resin composition for printing ink binder Download PDFInfo
- Publication number
- JP5130553B1 JP5130553B1 JP2012115512A JP2012115512A JP5130553B1 JP 5130553 B1 JP5130553 B1 JP 5130553B1 JP 2012115512 A JP2012115512 A JP 2012115512A JP 2012115512 A JP2012115512 A JP 2012115512A JP 5130553 B1 JP5130553 B1 JP 5130553B1
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- resin composition
- alcohol
- printing ink
- solvent
- 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.)
- Active
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- 238000007639 printing Methods 0.000 title claims abstract description 56
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 239000011230 binding agent Substances 0.000 title description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002009 diols Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 abstract description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000903 blocking effect Effects 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 3
- 239000002635 aromatic organic solvent Substances 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- -1 aromatic isocyanate Chemical class 0.000 description 18
- 239000012948 isocyanate Substances 0.000 description 14
- 239000003086 colorant Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000004970 Chain extender Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 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 6
- 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 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000005456 alcohol based solvent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003759 ester based solvent Substances 0.000 description 5
- 238000007646 gravure printing Methods 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
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 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 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
- 239000011248 coating agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 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
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 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
- 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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- VGHCVSPDKSEROA-UHFFFAOYSA-N 2-methyl-1,4-dioxecane-5,10-dione Chemical compound CC1COC(=O)CCCCC(=O)O1 VGHCVSPDKSEROA-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
- KTLIZDDPOZZHCD-UHFFFAOYSA-N 3-(2-aminoethylamino)propan-1-ol Chemical compound NCCNCCCO KTLIZDDPOZZHCD-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
- PXIPZIPSDBXFQR-UHFFFAOYSA-N 4,5-dimethyloxolan-2-one Chemical compound CC1CC(=O)OC1C PXIPZIPSDBXFQR-UHFFFAOYSA-N 0.000 description 1
- HDNIDWXLYXGKBI-UHFFFAOYSA-N 6-(2,2-dimethylpropoxy)-6-oxohexanoic acid Chemical compound CC(C)(C)COC(=O)CCCCC(O)=O HDNIDWXLYXGKBI-UHFFFAOYSA-N 0.000 description 1
- 102220566099 Antileukoproteinase_R45V_mutation Human genes 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
【課題】
トルエンやキシレンなどの芳香族有機溶剤、メチルエチルケトンやメチルイソブチルケトンなどのケトン系有機溶剤の排除に対応したエステル／アルコール溶剤系において、優れた版かぶり性等の印刷適性と、優れた耐ブロッキング性、接着性、耐アルコールブリード性等の印刷物性を両立したポリウレタン樹脂組成物使用の印刷インキ組成物を提供することにある。
【解決手段】
トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールとを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに、さらに、有機ジアミンおよびアルカノールアミンを反応させ、［ＮＣＯ（全）］／［ＯＨ］および［ＮＣＯ（ＴＤＩ）］／［ＯＨ］、ポリウレタン樹脂の水酸基価、有機ジアミンとアルカノールアミンとの比率を制御したポリウレタン樹脂、ならびにエステル系溶剤とアルコールとを含む混合溶剤を含むポリウレタン樹脂組成物を用いる。
【選択図】なし【Task】
In ester / alcohol solvent systems that are compatible with the elimination of aromatic organic solvents such as toluene and xylene, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, excellent printability such as plate fogging and excellent blocking resistance, An object of the present invention is to provide a printing ink composition using a polyurethane resin composition that has both printed and physical properties such as adhesion and alcohol bleed resistance.
[Solution]
A urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol is further reacted with an organic diamine and an alkanolamine, and [NCO (all)] / [OH] and A polyurethane resin composition containing [NCO (TDI)] / [OH], a polyurethane resin having a controlled hydroxyl value of polyurethane resin, a ratio of organic diamine to alkanolamine, and a mixed solvent containing an ester solvent and an alcohol is used. .
[Selection figure] None
Description
本発明は、印刷インキバインダー用ポリウレタン樹脂組成物および印刷インキ組成物に関し、さらに詳しくは、各種プラスチックフィルムに対し有用なポリウレタン樹脂組成物使用のエステル／アルコール溶剤系の印刷インキ組成物に関する。 The present invention relates to a polyurethane resin composition for printing ink binders and a printing ink composition, and more particularly to an ester / alcohol solvent based printing ink composition using a polyurethane resin composition useful for various plastic films.
従来、印刷インキで使用される溶剤としては、比較的溶解力の強いトルエンやキシレンなどの芳香族系の溶剤や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の溶剤が使用されてきた。しかし近年、地球規模での環境保全や法規制面から、印刷インキ業界へも、環境課題への配慮が要求されており、これらの芳香族系溶剤やケトン系溶剤を排除した、エステル／アルコール溶剤系を用いる印刷インキが望まれている。そのため、エステル／アルコール溶剤系の印刷インキの研究開発が行われてはいるが、エステル／アルコール溶剤系は芳香族系やケトン系の溶剤と比較し溶解力が低いため、印刷適性が悪かったり、エステル／アルコール溶剤への溶解力を上げる所作のため、耐アルコールブリード性や耐ブロッキング性などの他物性が劣ったりと、未だに課題が多い。 Conventionally, as solvents used in printing inks, aromatic solvents such as toluene and xylene having relatively high dissolving power and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone have been used. In recent years, however, the printing ink industry has been required to consider environmental issues from the viewpoint of environmental protection and legal regulations on a global scale. Ester / alcohol solvents that eliminate these aromatic and ketone solvents Printing inks using the system are desired. Therefore, research and development of printing inks based on ester / alcohol solvents has been carried out, but ester / alcohol solvent systems have lower solvency compared to aromatic and ketone solvents, resulting in poor printability, Due to the work to increase the dissolving power in the ester / alcohol solvent, other physical properties such as alcohol bleed resistance and blocking resistance are still inferior.
例えば、特開平９−３１６１５６公報では、ジフェニルメタンジイソシアネートを使用したポリウレタン樹脂組成物および印刷インキ組成物において、各種プラスチックフィルムに対し優れた接着性を有するが、印刷適性の確保のため、排除が求められているメチルエチルケトンを含む検討に留まっている。また、［ＮＣＯ］／［ＯＨ］比が低いため、耐ブロッキング性にも課題がある。 For example, in JP-A-9-316156, a polyurethane resin composition and a printing ink composition using diphenylmethane diisocyanate have excellent adhesion to various plastic films, but are required to be excluded in order to ensure printability. There are still studies involving methyl ethyl ketone. Moreover, since the [NCO] / [OH] ratio is low, there is also a problem in blocking resistance.
また、特開２００３−２２１５３９公報では、エステル／アルコール溶剤系でインキが組まれており、エステル／アルコール溶剤系への溶解性を上げる検討が行われているが、インキ中にヒドロキシカルボン酸が添加されているため、残留溶剤や耐水性、耐アルコールブリード性が劣る。 Japanese Patent Laid-Open No. 2003-221539 discloses that an ink is assembled in an ester / alcohol solvent system, and studies have been made to increase the solubility in the ester / alcohol solvent system. However, a hydroxycarboxylic acid is added to the ink. Therefore, residual solvent, water resistance and alcohol bleed resistance are inferior.
本発明は、トルエンやキシレンなどの芳香族有機溶剤、メチルエチルケトンやメチルイソブチルケトンなどのケトン系有機溶剤の排除に対応したエステル／アルコール溶剤系において、優れた版かぶり性等の印刷適性を確保し、かつ各種プラスチックフィルムに対し優れた接着性、耐ブロッキング性、耐アルコールブリード性、およびラミネート物性等の印刷物性をも併せ持つ印刷インキ組成物を提供することを目的とする。 In the ester / alcohol solvent system corresponding to the elimination of aromatic organic solvents such as toluene and xylene and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, the present invention ensures excellent printability such as plate fogging, It is another object of the present invention to provide a printing ink composition having excellent adhesion to various plastic films, blocking resistance, alcohol bleed resistance, and printed physical properties such as laminate physical properties.
本発明者らは、前記状況を鑑み鋭意検討を重ねた結果、イソシアネートにトリレンジイソシアネートを含むポリイソシアネート、さらに反応停止剤にアルカノールアミンを使用し、かつ合成パラメータを制御したポリウレタン樹脂を用いることで、比較的溶解力の弱いエステル／アルコール溶剤系において、優れた印刷適性と印刷物性の両立を達成したポリウレタン樹脂組成物を用いてなる印刷インキ組成物の設計を可能とすることを見出し、本発明に至った。 As a result of intensive studies in view of the above circumstances, the present inventors have used a polyisocyanate containing tolylene diisocyanate as an isocyanate, and a polyurethane resin using an alkanolamine as a reaction terminator and controlling the synthesis parameters. The present invention has found that it is possible to design a printing ink composition using a polyurethane resin composition that achieves both excellent printability and print properties in an ester / alcohol solvent system having a relatively weak dissolving power. It came to.
すなわち本発明の第一の発明は、トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールとを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーを、有機ジアミンおよびアルカノールアミンと反応させてなるポリウレタン樹脂、
並びに混合溶剤を含むポリウレタン樹脂組成物であって、
下記の（Ａ）〜（Ｆ）であることを特徴とするポリウレタン樹脂組成物に関するものである。
（Ａ）ポリイソシアネートの全イソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（全）］／［ＯＨ］が、１．８〜２．３である。
（Ｂ）トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が、１．０〜２．１である。
（Ｃ）ポリウレタン樹脂の水酸基価が１．０〜１０．０ｍｇＫＯＨ／ｇである。
（Ｄ）有機ジアミンのモル数ｄ１とアルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２が、３〜２５である。
（Ｅ）混合溶剤が、エステル系溶剤とアルコール系溶剤とを含む。
（Ｆ）高分子ポリオールが、ポリエステルジオールとポリエーテルジオールとからなる。
That is, the first invention of the present invention is a polyurethane resin obtained by reacting a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol with an organic diamine and an alkanolamine. ,
A polyurethane resin composition comprising a mixed solvent,
It is related with the polyurethane resin composition characterized by being the following (A)- (F) .
(A) The molar ratio [NCO (total)] / [OH] in the reaction of all isocyanate groups of the polyisocyanate and hydroxyl groups of the polymer polyol is 1.8 to 2.3.
(B) The molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol is 1.0 to 2.1.
(C) The hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
(D) The molar ratio d1 / d2 between the number of moles d1 of the organic diamine and the number of moles d2 of the alkanolamine is 3-25.
(E) The mixed solvent includes an ester solvent and an alcohol solvent.
(F) The polymer polyol is composed of a polyester diol and a polyether diol.
次に、第二の発明は、高分子ポリオールが、ポリエステルジオールとポリエーテルジオールとからなり、
高分子ポリオール中の、ポリエステルジオールが２０〜８０重量％、ポリエーテルジオール８０〜２０重量％であることを特徴とする請求項1記載のポリウレタン樹脂組成物に関するものである。
Next, in the second invention, the polymer polyol comprises a polyester diol and a polyether diol,
2. The polyurethane resin composition according to claim 1, wherein the polyester polyol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in the polymer polyol.
さらに、第三の発明は、第一発明または第二発明記載のポリウレタン樹脂組成物を含有することを特徴とする印刷インキ組成物に関するものである。 Furthermore, the third invention relates to a printing ink composition comprising the polyurethane resin composition described in the first invention or the second invention.
本発明は、エステル／アルコール溶剤系において優れた印刷適性を確保し、優れた印刷物性を保有するポリウレタン樹脂組成物使用の印刷インキ組成物を提供することを可能とする。 The present invention makes it possible to provide a printing ink composition using a polyurethane resin composition that ensures excellent printability in an ester / alcohol solvent system and possesses excellent print properties.
以下、印刷インキバインダー用ポリウレタン樹脂組成物について説明する。ポリウレタン樹脂は、トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに、鎖延長剤として有機ジアミン、反応停止剤としてアルカノールアミンを反応させて得られる。 Hereinafter, the polyurethane resin composition for a printing ink binder will be described. A polyurethane resin is obtained by reacting a polyisocyanate containing tolylene diisocyanate and a high molecular polyol with a urethane prepolymer having an isocyanate group at the terminal and an organic diamine as a chain extender and an alkanolamine as a reaction terminator. .
印刷インキバインダーに用いるポリウレタン樹脂において、エステル／アルコール溶剤への溶解力と、種々のプラスチックフィルムに対する各種印刷物性の両立を考慮する場合、重要な因子となるのが、ウレタン結合、ウレア結合のハードセグメントを形成するポリイソシアネートである。 In polyurethane resins used as printing ink binders, when considering the compatibility between the solubility in ester / alcohol solvents and various printed physical properties for various plastic films, the important factors are the hard segments of urethane bonds and urea bonds. Is a polyisocyanate.
本発明において、ポリウレタン樹脂で用いるポリイソシアネートは、トリレンジイソシアネートを含み、ＴＤＩと表記されることもある。トリレンジイソシアネートは、２，４−トリレンジイソシアネートまたは、２，６−トリレンジイソシアネートが好ましく、２，４−トリレンジイソシアネートと２，６−トリレンジイソシアネートとを混合して使用してもよい。 In the present invention, the polyisocyanate used in the polyurethane resin contains tolylene diisocyanate and may be expressed as TDI. Tolylene diisocyanate is preferably 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate, and 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate may be mixed and used.
トリレンジイソシアネートは分子内に芳香族環を一つ有する芳香族イソシアネートであるため、脂肪族イソシアネートや脂環族イソシアネートと比較し、よりアルコールへの耐性が高い。一方で、芳香族環を二つ有する芳香族イソシアネートであるジフェニルメタンジイソシアネートと比較し、トリレンジイソシアネートは芳香族環が一つであるため、エステル／アルコール溶剤系への溶解力が高い。よって、トリレンジイソシアネートはエステル／アルコール溶剤系の印刷インキ組成物において、版かぶり性等の印刷適性と耐アルコールブリード性のバランスを取りやすいポリイソシアネートであると言える。 Since tolylene diisocyanate is an aromatic isocyanate having one aromatic ring in the molecule, it has higher resistance to alcohol than aliphatic isocyanates and alicyclic isocyanates. On the other hand, as compared to diphenylmethane diisocyanate, which is an aromatic isocyanate having two aromatic rings, tolylene diisocyanate has a single aromatic ring and therefore has a higher solubility in an ester / alcohol solvent system. Therefore, it can be said that tolylene diisocyanate is a polyisocyanate that easily balances printing suitability such as plate fog and alcohol bleed resistance in an ester / alcohol solvent-based printing ink composition.
本発明において、トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーを合成する際、ポリイソシアネートと高分子ポリオールの水酸基との全イソシアネート基のモル比率である［ＮＣＯ（全）］／［ＯＨ］が、１．８〜２．３の範囲にある。［ＮＣＯ（全）］／［ＯＨ］が１．８より小さいとハードセグメント結合数が少なくなるため耐ブロッキング性、耐アルコールブリード性が劣り、２．３より大きいと版かぶり性が劣り、またハードセグメント結合数が多くなりすぎるため接着性、ＥＬラミネート強度が劣る。 In the present invention, when synthesizing a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol, the molar ratio of all isocyanate groups of the polyisocyanate and the hydroxyl group of the polymer polyol. [NCO (all)] / [OH] is in the range of 1.8 to 2.3. If [NCO (all)] / [OH] is less than 1.8, the number of hard segment bonds decreases, so that the blocking resistance and alcohol bleed resistance are inferior. If it is greater than 2.3, the plate fogging property is inferior. Adhesiveness and EL laminate strength are inferior because the number of segment bonds is too large.
本発明において、トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比率である［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が、１．０〜２．１の範囲にある。一般的に芳香族イソシアネートは、脂肪族イソシアネートや脂環族イソシアネートと比較し、水酸基やアミノ基との反応速度が速い。よって、［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が２．１より大きいと、反応速度が速すぎるため均一なポリウレタン樹脂合成ができず、さらには、分子内の芳香族環濃度の高さから版かぶり性が劣る。また、［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が１．０より小さいと耐アルコールブリード性が劣る。 In the present invention, [NCO (TDI)] / [OH], which is a molar ratio in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol, is in the range of 1.0 to 2.1. In general, an aromatic isocyanate has a higher reaction rate with a hydroxyl group or an amino group than an aliphatic isocyanate or an alicyclic isocyanate. Therefore, when [NCO (TDI)] / [OH] is greater than 2.1, the reaction rate is too high to synthesize a uniform polyurethane resin, and further, the plate has a high concentration of aromatic rings in the molecule. Poor fogging property. Further, when [NCO (TDI)] / [OH] is smaller than 1.0, the alcohol bleeding resistance is inferior.
なお、上記の［ＮＣＯ（全）］／［ＯＨ］および［ＮＣＯ（ＴＤＩ）］／［ＯＨ］を満たす範囲であれば、トリレンジイソシアネート以外に他のポリイソシアネートを併用してもよい。他のポリイソシアネートとしては、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脂肪族イソシアネート、脂環族イソシアネートが挙げられる。例えば、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、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、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、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。本発明においては、他のポリイソシアネートの中でも、イソシアネート基の反応速度および諸々の物性の観点からイソホロンジイソシアネートが好ましい。 In addition to the tolylene diisocyanate, another polyisocyanate may be used in combination as long as it satisfies the above [NCO (all)] / [OH] and [NCO (TDI)] / [OH]. Examples of other polyisocyanates include various known aliphatic isocyanates and alicyclic isocyanates that are generally used in the production of polyurethane resins. For example, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimaryl diisocyanate, Examples thereof include dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. In the present invention, among other polyisocyanates, isophorone diisocyanate is preferred from the viewpoint of the reaction rate of the isocyanate group and various physical properties.
さらに、上記の［ＮＣＯ（全）］／［ＯＨ］および［ＮＣＯ（ＴＤＩ）］／［ＯＨ］を満たす範囲であり、かつ、全イソシアネート基のモル数中の９０〜１００％がトリレンジイソシアネートから、１０〜０％がイソホロンジイソシアネートからである場合、耐アルコールブリード性に特に優れる。また、同様に全イソシアネート基のモル数中の５０〜７５％がトリレンジイソシアネートから、５０〜２５％がイソホロンジイソシアネートからである場合、印刷インキ組成物に含まれる溶剤のうち、３５％以上がアルコール系溶剤となった場合の版かぶり性に特に優れる。なお、印刷インキ組成物に含まれる混合溶剤の詳細については後述する。 Furthermore, the range satisfying the above [NCO (all)] / [OH] and [NCO (TDI)] / [OH], and 90 to 100% in the number of moles of all isocyanate groups is from tolylene diisocyanate. When the content is 10 to 0% from isophorone diisocyanate, the alcohol bleeding resistance is particularly excellent. Similarly, when 50 to 75% of the total number of isocyanate groups is from tolylene diisocyanate and 50 to 25% is from isophorone diisocyanate, 35% or more of the solvent contained in the printing ink composition is alcohol. It is particularly excellent in plate fog when it becomes a solvent. The details of the mixed solvent contained in the printing ink composition will be described later.
さらに、エステル／アルコール溶剤系での版かぶり性等の印刷適性と、耐アルコールブリード性のバランスを取るために重要な因子として、ポリウレタン樹脂の水酸基価がある。本発明におけるポリウレタン樹脂の水酸基価は１．０〜１０．０ｍｇＫＯＨ／ｇである。水酸基価が１．０ｍｇＫＯＨ／ｇ未満であると、接着性、ＥＬラミネート強度が劣り、また溶解性も著しく悪化するため版かぶり性が劣る。水酸基価が１０．０ｍｇＫＯＨ／ｇより大きいと、耐アルコールブリード性が劣る。 Furthermore, the hydroxyl value of the polyurethane resin is an important factor for balancing printing suitability such as plate fog in an ester / alcohol solvent system and alcohol bleed resistance. The hydroxyl value of the polyurethane resin in the present invention is 1.0 to 10.0 mgKOH / g. When the hydroxyl value is less than 1.0 mgKOH / g, the adhesiveness and EL laminate strength are inferior, and the solubility is remarkably deteriorated, so that the plate fog is inferior. When the hydroxyl value is greater than 10.0 mgKOH / g, the alcohol bleed resistance is poor.
本発明における鎖延長剤としての有機ジアミンは、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、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が、特にイソホロンジアミンが好ましい。 The organic diamine as a chain extender in the present invention is ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, etc., 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2 -Amines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine can also be used. These chain extenders can be used alone or in admixture of two or more, and isophoronediamine is particularly preferred.
本発明におけるポリウレタン樹脂の有機ジアミンのモル数ｄ１と、アルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２が、３〜２５である。ｄ１／ｄ２が３より小さいと、耐アルコールブリード性が劣り、またポリウレタン樹脂の重量平均分子量が小さくなるため耐ブロッキング性も著しく悪化する。ｄ１／ｄ２が２５より大きいと、接着性、ＥＬラミネート強度が劣り、また溶解性も著しく悪化するため版かぶり性が劣る。 In the present invention, the molar ratio d1 / d2 between the number of moles d1 of the organic diamine of the polyurethane resin and the number of moles d2 of the alkanolamine is 3-25. When d1 / d2 is smaller than 3, the alcohol bleed resistance is inferior, and the weight average molecular weight of the polyurethane resin is reduced, so that the blocking resistance is remarkably deteriorated. When d1 / d2 is larger than 25, the adhesiveness and EL laminate strength are inferior, and the solubility is also greatly deteriorated, so that the plate fogging property is inferior.
なお、反応停止剤であるアルカノールアミンの使用量が多くなると、得られるポリウレタン樹脂の重量平均分子量は低くなる。また、アルカノールアミンには水酸基が含まれているため、アルカノールアミンの使用量が多くなると、水酸基価は大きくなる。アルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン等が挙げられる。これらは単独で、または２種以上を混合して用いることができるが、特にモノエタノールアミンが好ましい。 In addition, when the usage-amount of alkanolamine which is a reaction terminator increases, the weight average molecular weight of the polyurethane resin obtained will become low. Further, since the alkanolamine contains a hydroxyl group, the hydroxyl value increases as the amount of alkanolamine used increases. Examples of the alkanolamine include monoethanolamine and diethanolamine. These can be used alone or in admixture of two or more, and monoethanolamine is particularly preferred.
高分子ポリオールとしては各種公知のポリエステルポリオール、ポリエーテルポリオール等を用いることができ、それぞれ１種または２種以上を併用してもよい。ポリエステルポリオールとしては、例えば、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、２メチル−１，３プロパンジオール、２エチル−２ブチル−１，３プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３−メチル−１，５ペンタンジオール、ヘキサンジオール、オクタンジオール、１，４−ブチンジオール、１，４−ブチレンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、１，２，６−ヘキサントリオール、１，２，４−ブタントリオール、ソルビトール、ペンタエスリトールなどの飽和または不飽和の低分子ポリオール類と、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、こはく酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、トリメリット酸、ピロメリット酸などの多価カルボン酸あるいはこれらの無水物とを脱水縮合または重合させて得られるポリエステルポリオール類、環状エステル化合物、例えばポリカプロラクトン、ポリバレロラクトン、ポリ（β−メチル−γ−バレロラクトン）等のラクトン類、を開環重合して得られるポリエステルポリオール類などが挙げられる。ポリエーテルポリオールとしては、例えば酸化メチレン、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が挙げられる。ポリエステルポリオールにおいても、ポリエーテルポリオールにおいても分岐構造を持つものが特に好ましい。 Various known polyester polyols, polyether polyols, and the like can be used as the polymer polyol, and one or more of them may be used in combination. Examples of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3-propanediol, 2ethyl-2butyl-1,3propanediol, and 1,3-butane. Diol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene Saturated or unsaturated low molecular weight polyols such as glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaerythritol Kind , Adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid Polyester polyols obtained by dehydration condensation or polymerization of these polyhydric carboxylic acids or their anhydrides, cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone), etc. And polyester polyols obtained by ring-opening polymerization of lactones. Examples of polyether polyols include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. Of polyester polyols and polyether polyols, those having a branched structure are particularly preferred.
本発明におけるポリウレタン樹脂に用いる高分子ポリオールはポリエステルジオールとポリエーテルジオールを用い、高分子ポリオール中のポリエステルジオールが２０〜８０重量％、ポリエーテルジオール８０〜２０重量％の範囲にあるのが好ましい。ポリエステルジオールが８０重量％より多いと版かぶり性が悪化する傾向が見られ、ポリエーテルジオールが８０重量％より多いと耐ブロッキング性が劣る傾向が見られる。 The polymer polyol used for the polyurethane resin in the present invention is a polyester diol and a polyether diol, and the polyester diol in the polymer polyol is preferably in the range of 20 to 80% by weight and the polyether diol in the range of 80 to 20% by weight. When the polyester diol is more than 80% by weight, the plate fogging tendency tends to be deteriorated, and when the polyether diol is more than 80% by weight, the blocking resistance tends to be inferior.
本発明におけるポリウレタン樹脂のアミン価は２．０〜７．０ｍｇＫＯＨ／ｇ、より好ましくは３．０〜６．０ｍｇＫＯＨ／ｇである。アミン価が２．０ｍｇＫＯＨ／ｇより小さいと版かぶり性、接着性およびＥＬラミネート強度が劣りやすく、７．０ｍｇＫＯＨ／ｇより大きいと耐ブロッキング性が劣りやすい。 The amine value of the polyurethane resin in the present invention is 2.0 to 7.0 mgKOH / g, more preferably 3.0 to 6.0 mgKOH / g. If the amine value is less than 2.0 mgKOH / g, the plate fogging property, adhesiveness and EL laminate strength tend to be inferior, and if it is more than 7.0 mgKOH / g, the blocking resistance tends to be inferior.
本発明におけるポリウレタン樹脂の重量平均分子量は１００００〜７００００、より好ましくは１５０００〜６００００である。重量平均分子量が１００００より小さいと耐ブロッキング性が劣りやすく、また耐熱性が悪化するためＥＬラミネート強度も劣りやすい。重量平均分子量が７００００より大きいと、版かぶり性、接着性およびＥＬラミネート強度が劣りやすい。 The weight average molecular weight of the polyurethane resin in the present invention is 10,000 to 70,000, more preferably 15,000 to 60,000. When the weight average molecular weight is less than 10,000, the blocking resistance tends to be inferior, and the heat resistance deteriorates, so the EL laminate strength tends to be inferior. When the weight average molecular weight is more than 70,000, the plate fogging property, adhesiveness and EL laminate strength tend to be inferior.
本発明におけるポリウレタン樹脂の合成法は、高分子ポリオールとトリレンジイソシアネートを含むポリイソシアネートを、必要に応じイソシアネート基に不活性な溶媒を用い、また、更に必要であればウレタン化触媒を用いて１０〜１００℃の温度で反応させ、末端にイソシアネート基を有するプレポリマーを製造し、次いで、このプレポリマーに鎖延長剤として有機ジアミン、反応停止剤としてアルカノールアミンを１０〜８０℃で反応させるポリウレタン樹脂を得るプレポリマー法から製造することが出来る。 In the method of synthesizing a polyurethane resin in the present invention, a polyisocyanate containing a polymer polyol and tolylene diisocyanate is used, if necessary, using an inert solvent for the isocyanate group, and if necessary, using a urethanization catalyst. A polyurethane resin in which a prepolymer having an isocyanate group at the terminal is produced by reacting at a temperature of ˜100 ° C., and then this prepolymer is reacted with an organic diamine as a chain extender and an alkanolamine as a reaction terminator at 10 to 80 ° C. Can be produced from a prepolymer method.
本発明のポリウレタン樹脂組成物に使用される溶剤は、エステル系溶剤とアルコール系溶剤の混合溶剤を含む。エステル系溶剤としては、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸イソブチル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなど、アルコール系溶剤としては、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、ｎ−ブタノール、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのアルコール系溶剤など公知の溶剤を使用することが好ましい。 The solvent used in the polyurethane resin composition of the present invention includes a mixed solvent of an ester solvent and an alcohol solvent. Examples of ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and alcohol solvents include methanol, ethanol, n-propanol, isopropanol, It is preferable to use a known solvent such as an alcohol solvent such as n-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether.
ウレタン化反応には触媒を用いることもできる。使用できる触媒としては、例えば、トリエチルアミン、ジメチルアニリンなどの３級アミン系の触媒；スズ、亜鉛などの金属系の触媒などが挙げられる。これらの触媒は通常ポリオールに対して０．００１〜１モル％の範囲で使用される。 A catalyst can also be used for the urethanization reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol.
反応停止剤であるアルカノールアミンと、鎖延長剤である有機ジアミンとは一緒に使用して鎖延長反応を行ってもよく、また鎖延長剤によりある程度鎖延長反応を行った後に反応停止剤を単独に添加して反応停止反応を行ってもよい。 The chain extender may be used together with the alkanolamine, which is a reaction terminator, and the organic diamine, which is a chain extender. May be added to the reaction to stop the reaction.
本発明の印刷インキ組成物には、着色剤として無機系着色剤および有機系着色剤を使用できる。白色着色剤には、無機系着色剤である酸化チタンを使用するが、顔料表面が塩基性であるものがより好ましい。無機系着色剤として白色着色剤以外には、カーボンブラック、アルミニウム、マイカ（雲母）などの顔料が挙げられる。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。一方、有機系着色剤としては、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、顔料や染料を挙げることができる。例えば、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が挙げられる。 In the printing ink composition of the present invention, an inorganic colorant and an organic colorant can be used as the colorant. As the white colorant, titanium oxide, which is an inorganic colorant, is used, but it is more preferable that the pigment surface is basic. In addition to the white colorant, pigments such as carbon black, aluminum, mica (mica) and the like can be used as the inorganic colorant. 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. On the other hand, examples of organic colorants include organic, pigments, and dyes used in general inks, paints, and recording agents. Examples thereof include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline.
着色剤は、印刷インキの濃度・着色力を確保するのに充分な量、すなわち印刷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、これらの着色剤は単独で、または２種以上を併用して用いることができる。 The colorant is preferably contained in an amount sufficient to ensure the density and coloring power of the printing ink, that is, in a proportion of 1 to 50% by weight with respect to the total weight of the printing ink. These colorants can be used alone or in combination of two or more.
本発明の印刷インキ組成物は、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、顔料を本発明のポリウレタン樹脂組成物、必要に応じて他の化合物などを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本発明のポリウレタン樹脂組成物、有機溶剤、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 printing ink composition of the present invention can be produced by dissolving and / or dispersing a resin, a colorant and the like in an organic solvent. Specifically, the polyurethane resin composition of the present invention is manufactured by dispersing the pigment in the polyurethane resin composition of the present invention and, if necessary, other compounds and the like in an organic solvent. An ink can be produced by blending a product, an organic solvent, and other compounds as required.
顔料を有機溶剤に安定に分散させるには、本発明におけるポリウレタン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重量％以上、かつ、ラミネート適性の観点から５重量％以下でインキ中に含まれることが好ましい。さらに、０．１〜２重量％の範囲で含まれることがより好ましい。 In order to stably disperse the pigment in the organic solvent, the polyurethane resin in the present invention can be dispersed alone, but a dispersant can also be used in combination 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% by weight or more based on the total weight of the ink from the viewpoint of the storage stability of the ink and 5% by weight or less from the viewpoint of the suitability for lamination. Furthermore, it is more preferable that it is contained in the range of 0.1 to 2% by weight.
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.
本発明の印刷インキ組成物に使用される溶剤についても、ポリウレタン樹脂組成物と同様、エステル系溶剤とアルコール系溶剤の混合溶剤を含む。エステル系溶剤としては、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸イソブチル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなど、アルコール系溶剤としては、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、ｎ−ブタノール、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのアルコール系溶剤など公知の溶剤を使用することが好ましい。 The solvent used in the printing ink composition of the present invention also includes a mixed solvent of an ester solvent and an alcohol solvent, like the polyurethane resin composition. Examples of ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and alcohol solvents include methanol, ethanol, n-propanol, isopropanol, It is preferable to use a known solvent such as an alcohol solvent such as n-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether.
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の粘度は、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 viscosity of the ink 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. Is preferred. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
本発明における印刷インキ組成物は、グラビア印刷、フレキソ印刷などの既知の印刷方式で用いることができる。例えば、グラビア印刷に適した粘度およ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。好ましくは、グラビア印刷である。 The printing ink composition in the present invention can be used in known printing methods such as gravure printing and flexographic printing. For example, it is diluted with a diluent solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed. Gravure printing is preferable.
本発明の印刷インキ組成物を適用できる基材としては、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリエチレンテレフタレート、ポリカーボネート、ポリ乳酸などのポリエステル、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂などのポリスチレン系樹脂、ナイロン、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、セロハン、紙、アルミなど、もしくはこれらの複合材料からなるフィルム状もしくはシート状のものがあり、上記の印刷方式を用いて塗布し、オーブンによる乾燥によって乾燥させて定着することで、印刷物を得ることができる。基材は、金属酸化物などを表面に蒸着コート処理および／またはポリビニルアルコールなどコート処理が施されていても良く、さらにコロナ処理などの表面処理が施されていても良い。 As a substrate to which the printing ink composition of the present invention can be applied, polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, polyester such as polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, Polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or a film or sheet made of a composite material of these, is applied using the printing method described above, dried by oven drying, and fixed. By doing so, a printed matter can be obtained. The base material may be subjected to a metal oxide or the like on its surface by a vapor deposition coating treatment and / or a coating treatment such as polyvinyl alcohol, and may further be subjected to a surface treatment such as a corona treatment.
本発明の印刷インキ組成物を印刷した印刷物を、ラミネート加工を施しエージングすれば、ラミネート積層体が得られる。ラミネート加工法としては１）得られた印刷物の印刷面に、必要に応じてアンカーコート剤を塗布後、溶融樹脂を積層する押し出しラミネート法、２）接着剤を塗布後、必要に応じて乾燥させプラスチックフィルムを積層するドライラミネート法等が挙げられる。溶融樹脂としては低密度ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体等が使用でき、接着剤としてはイミン系、イソシアネート系、ポリブタジエン系、チタネート系等が挙げられる。 If the printed matter obtained by printing the printing ink composition of the present invention is subjected to laminating and aging, a laminate laminate is obtained. The laminating method is as follows: 1) Extrusion laminating method in which a molten resin is laminated after applying an anchor coating agent on the printed surface of the obtained printed material, if necessary. 2) After applying an adhesive, it is dried if necessary. Examples include a dry laminating method in which plastic films are laminated. As the molten resin, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used, and as the adhesive, imine, isocyanate, polybutadiene, titanate and the like can be mentioned.
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。なお、本発明における部および％は、特に注釈の無い場合、重量部および重量％を表す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise noted.
なお、水酸基価は、樹脂中の水酸基を過剰のアセチル化試薬にてアセチル化し、残存する酸をアルカリで逆滴定して算出した樹脂１ｇ中の水酸基量を、水酸化カリウムのｍｇ数に換算した値で、ＪＩＳ Ｋ００７０に従って行った値である。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の当量と同量の水酸化カリウムのｍｇ数である。酸価は、樹脂１ｇ中に含有する酸基を中和するのに必要とする水酸化カリウムのｍｇ数で、測定方法は既知の方法でよく、一般的にはＪＩＳ Ｋ００７０（１９９６年）に準じて行われる。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。アミン価の測定方法は、下記の通りである。 The hydroxyl value was acetylated with an excess of an acetylating reagent and the amount of hydroxyl group in 1 g of resin calculated by back titrating the remaining acid with alkali was converted to mg of potassium hydroxide. The value is a value obtained according to JIS K0070. The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of resin, and the measurement method may be a known method, generally according to JIS K0070 (1996). Done. The molecular weight was determined as a polystyrene-converted molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus. 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（ＡｍＬ）を用い次の（式１）によりアミン価を求めた。
[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 1) using the titration amount (AmL) at this time.
計算式１
アミン価＝（Ａ×ｆ×０．２×５６．１０８）／Ｓ ［ｍｇＫＯＨ／ｇ］
Formula 1
Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]
［合成例１］
攪拌機、温度計、還流冷却器および窒素ガス導入管を備えた四つ口フラスコに、分子量２０００のＰＰＡ２０００（水酸基価５６．１ｍｇＫＯＨ／ｇ）１１１．９９部、分子量１０００のＰＰＧ１０００（水酸基価１１２．２ｍｇＫＯＨ／ｇ）１１１．９９部、トリレンジイソシアネート５２．６５部、２−エチルヘキサン酸スズ（II）０．０３部、酢酸エチル８２．５部を仕込み、窒素気流下に９０℃で３時間反応させ、末端イソシアネートプレポリマーの溶液３５９．１６部を得た。次いでイソホロンジアミン２１．７４部、モノエタノールアミン１．６４部、イソプロピルアルコール２９０部、酢酸エチル３２７．４７部を混合したものへ、得られた末端イソシアネートプレポリマーの溶剤溶液３５９．１６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３０．０％、重量平均分子量３００００、アミン価４．０ｍｇＫＯＨ／ｇのポリウレタン樹脂組成物（ＰＵ０１）を得た。
[Synthesis Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, PPA2000 (hydroxyl value 56.1 mgKOH / g) with a molecular weight of 2000. 111.99 parts, PPG1000 with a molecular weight of 1000 (hydroxyl value 112.2 mgKOH) / G) 111.99 parts, 52.65 parts of tolylene diisocyanate, 0.03 part of tin (II) 2-ethylhexanoate, and 82.5 parts of ethyl acetate were allowed to react at 90 ° C. for 3 hours under a nitrogen stream. 359.16 parts of a terminal isocyanate prepolymer solution were obtained. Next, 359.16 parts of the solvent solution of the resulting terminal isocyanate prepolymer was mixed at room temperature with 21.74 parts of isophoronediamine, 1.64 parts of monoethanolamine, 290 parts of isopropyl alcohol, and 327.47 parts of ethyl acetate. The mixture was gradually added and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin composition (PU01) having a solid content of 30.0%, a weight average molecular weight of 30000, and an amine value of 4.0 mgKOH / g.
［合成例２〜２４］
表１および表２の仕込み比にて、合成例１と同様の操作で、ポリウレタン樹脂組成物（ＰＵ０２〜ＰＵ２４）を得た。
なお合成には下記の原料を用いた。
ＰＰＡ２０００：ポリ（１，２−プロピレンアジペート）ジオール（数平均分子量２０００）
ＮＰＧ２０００：ポリ（ネオペンチルアジペート）ジオール（数平均分子量２０００）
ＰＭＰＡ２０００：ポリ（３−メチル−１，５−ペンタンアジペート）ジオール（数平均分子量２０００）
ＰＰＧ１０００：ポリ（１，２−プロピレングリコール）（数平均分子量１０００）
ＴＤＩ：トリレンジイソシアネート
ＩＰＤＩ：イソホロンジイソシアネート
ＭＤＩ：ジフェニルメタンジイソシアネート
ＩＰＤＡ：イソホロンジアミン
ＭＥＡ：モノエタノールアミン
ＤＥＡ：ジエタノールアミン
ＤＢＡ：ジ−ｎ−ブチルアミン
ＩＰＡ：イソプロピルアルコール
[Synthesis Examples 2 to 24]
A polyurethane resin composition (PU02 to PU24) was obtained in the same manner as in Synthesis Example 1 with the charging ratios in Table 1 and Table 2.
The following raw materials were used for the synthesis.
PPA2000: poly (1,2-propylene adipate) diol (number average molecular weight 2000)
NPG2000: poly (neopentyl adipate) diol (number average molecular weight 2000)
PMPA2000: poly (3-methyl-1,5-pentaneadipate) diol (number average molecular weight 2000)
PPG1000: poly (1,2-propylene glycol) (number average molecular weight 1000)
TDI: Tolylene diisocyanate IPDI: Isophorone diisocyanate MDI: Diphenylmethane diisocyanate IPDA: Isophoronediamine MEA: Monoethanolamine DEA: Diethanolamine DBA: Di-n-butylamine IPA: Isopropyl alcohol
［実施例１］
酸化チタン（ＴＩＴＯＮＥ Ｒ４５Ｍ 堺化学製）３０．００部、ポリウレタン樹脂組成物（ＰＵ０１）１０．００部、酢酸エチル／イソプロピルアルコール混合溶剤（重量比７０／３０）１０．００部を撹拌混合しサンドミルで練肉した後、ポリウレタン樹脂組成物（ＰＵ０１）４０．００部、酢酸エチル／イソプロピルアルコール混合溶剤（重量比７０／３０）１０．００部を攪拌混合し、白色印刷インキ組成物（Ｗ０１）を得た。さらに、この白色印刷インキ組成物１００．００部に、重量比で酢酸エチル／イソプロピルアルコール＝８５／１５の希釈溶剤１、または酢酸エチル／イソプロピルアルコール＝５０／５０の希釈溶剤２を、それぞれ４０．００部混合し、評価用の白色希釈印刷インキ１および白色希釈印刷インキ２とした。
[Example 1]
30.00 parts of titanium oxide (TITONE R45M manufactured by Sakai Chemical Co., Ltd.), 10.00 parts of polyurethane resin composition (PU01), 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were stirred and mixed in a sand mill. After kneading, 40.00 parts of polyurethane resin composition (PU01) and 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were mixed by stirring to obtain a white printing ink composition (W01). It was. Further, 100.00 parts of this white printing ink composition was diluted by 40. respectively with a dilution solvent 1 of ethyl acetate / isopropyl alcohol = 85/15 or a dilution solvent 2 of ethyl acetate / isopropyl alcohol = 50/50 by weight ratio. 00 parts were mixed to obtain white diluted printing ink 1 and white diluted printing ink 2 for evaluation.
［実施例２〜１６］［比較例１〜８］
実施例１と同様の操作で、白色印刷インキ組成物（Ｗ０２〜１６及びＷ１７〜２４）を得た。なお、各々の印刷インキ組成物に用いるポリウレタン樹脂組成物は表３および表４の通りである。また、実施例１と同様の操作で、得られた白色印刷インキ組成物１００．００部に、重量比で酢酸エチル／イソプロピルアルコール＝８５／１５の希釈溶剤１、または酢酸エチル／イソプロピルアルコール＝５０／５０の希釈溶剤２を、それぞれ４０．００部混合し、評価用の白色希釈印刷インキ１および白色希釈印刷インキ２とした。
[Examples 2 to 16] [Comparative Examples 1 to 8]
White printing ink compositions (W02 to 16 and W17 to 24) were obtained by the same operation as in Example 1. In addition, the polyurethane resin composition used for each printing ink composition is as Table 3 and Table 4. Further, by the same operation as in Example 1, 100.00 parts of the obtained white printing ink composition was diluted with a diluent 1 having a weight ratio of ethyl acetate / isopropyl alcohol = 85/15, or ethyl acetate / isopropyl alcohol = 50. 40.00 parts each of / 50 dilution solvent 2 was mixed to obtain white diluted printing ink 1 and white diluted printing ink 2 for evaluation.
［版かぶり性］
ＮＢＲ（ニトリルブタジエンゴム）製のゴム硬度８０Ｈｓの圧胴、刃先の厚みが６０μｍ（母材の厚み４０μｍ、片側セラミック層の厚み１０μｍ）のセラミックメッキドクターブレード、東洋プリプレス株式会社製のクロム硬度１０５０Ｈｖの電子彫刻版（スタイラス角度１２０度、２００線／ｉｎｃｈ）の富士機械工業株式会社製グラビア印刷機に白色希釈印刷インキ１または白色希釈印刷インキ２をセットし、ドクター圧２ｋｇ／ｃｍ２、１００ｍ／分の回転速度で空転を６０分行った後、片面コロナ処理ＯＰＰフィルム「パイレンＰ−２１６１（東洋紡績株式会社製）」のコロナ処理面に、印刷速度１００ｍ／分で印圧２ｋｇ／ｃｍ２、６０℃の熱風で乾燥し、印刷物を得た。この印刷物を黒色の紙の上に貼り、余白部分（非画線部）に付着したインキの量を以下の基準で目視評価した。
◎ ：非画像部にインキの転移が全く認められなかった。
○ ：非画像部にインキの転移が僅かに認められた。
○△：非画像部の小面積にインキの転移が認められた。これ以上実用レベルである。
△ ：非画像部の大面積にインキの転移が認められた。
× ：非画像部全面にインキの転移が認められた。
[Plate fog]
An NBR (nitrile butadiene rubber) rubber hardness 80Hs impression cylinder, a blade thickness of 60 μm (base material thickness 40 μm, one side ceramic layer thickness 10 μm), a chrome hardness 1050 Hv made by Toyo Prepress Co., Ltd. The white diluted printing ink 1 or the white diluted printing ink 2 is set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd. with an electronic engraving plate (stylus angle 120 degrees, 200 lines / inch), doctor pressure 2 kg / cm 2, 100 m / min. After idling at a rotational speed for 60 minutes, on a corona-treated surface of a single-sided corona-treated OPP film “Pyrene P-2161 (manufactured by Toyobo Co., Ltd.)”, at a printing speed of 100 m / min, a printing pressure of 2 kg / cm 2 and 60 ° C. It was dried with hot air to obtain a printed matter. This printed matter was pasted on black paper, and the amount of ink attached to the blank portion (non-image area) was visually evaluated according to the following criteria.
A: No ink transfer was observed in the non-image area.
○: Slight ink transfer was observed in the non-image area.
○ Δ: Ink transfer was observed in a small area of the non-image area. More practical than that.
Δ: Ink transfer was observed in a large area of the non-image area.
X: Ink transfer was observed over the entire non-image area.
［耐ブロッキング性］
白色希釈印刷インキ１を、版深３５μｍグラビア版を備えたグラビア校正機によるコロナ処理ＯＰＰフィルム（太閤ＦＯＲ フタムラ ＃２０）に印刷して４０〜５０℃で乾燥し、印刷物を得た。この印刷物を４ｃｍ×４ｃｍにサンプリングし、このサンプルの印刷面と同じ大きさの未印刷フィルムの非処理面とを合わせて、５０℃１２時間、１０ｋｇｆの加圧を行い、サンプルを剥離した時の、インキ取られ及び抵抗感を観察した。
◎ ：印刷物からインキの転移が全く認められず、剥離時の抵抗感もなかった。
○ ：印刷物からインキの転移が全く認められなかったが、剥離時の抵抗感があった。
○△：印刷物からインキの転移が認められたが、面積にして１０％未満であった。
これ以上実用レベルである。
△ ：印刷物からインキの転移が、１０％以上５０％未満の面積で認められた。
× ：印刷物からインキの転移が、５０％以上の面積で認められた。
[Blocking resistance]
The white diluted printing ink 1 was printed on a corona-treated OPP film (Taiko FOR-Futamura # 20) by a gravure proofing machine equipped with a gravure plate having a plate depth of 35 μm and dried at 40 to 50 ° C. to obtain a printed matter. This printed matter was sampled to 4 cm × 4 cm, and the unprinted surface of the unprinted film having the same size as the printed surface of this sample was combined and pressurized at 50 ° C. for 12 hours and 10 kgf, and the sample was peeled off. The ink was removed and the resistance was observed.
A: Ink transfer from the printed matter was not observed at all, and there was no resistance when peeled.
○: No transfer of ink was observed from the printed matter, but there was a feeling of resistance during peeling.
◯: Ink transfer was observed from the printed matter, but the area was less than 10%.
More practical than that.
Δ: Ink transfer from the printed material was observed in an area of 10% or more and less than 50%.
X: Ink transfer from the printed matter was observed in an area of 50% or more.
［接着性］
耐ブロッキング性試験で得た印刷物にセロハンテープ（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。
◎ ：ゆっくり引き離しても、急激に引き離しても全くインキの剥離が認められない。
○ ：ゆっくり引き離しても全くインキの剥離は認められないが、
急激に引き離すとインキの剥離が２０％未満の面積で認められた。これ以上実用レベルである。
△ ：ゆっくり引き離してもインキの剥離は認められないが、
急激に引き離すとインキの剥離が２０％以上の面積で認められた。
△×：ゆっくり引き離しても５０％程度までの面積のインキの剥離が認められた。
× ：ゆっくり引き離してもほとんどのインキの剥離が認められた。
[Adhesiveness]
A cellophane tape (made by Nichiban, width 12 mm) is affixed to the printed matter obtained in the blocking resistance test and rubbed strongly with the thumb 5 times. Examined.
A: No peeling of ink was observed even when pulled apart slowly or suddenly.
○: Ink peeling is not observed at all even if pulled slowly,
When peeled off rapidly, ink peeling was observed in an area of less than 20%. More practical than that.
△: Ink peeling is not observed even if pulled slowly,
When peeled off rapidly, ink peeling was observed in an area of 20% or more.
Δ ×: Ink peeling with an area of up to about 50% was observed even when slowly separated.
X: Most ink peeling was recognized even if it pulled away slowly.
［耐アルコールブリード性］
白色希釈印刷インキ１を、版深３５μｍグラビア版を備えたグラビア校正機によるコロナ処理ＯＰＰフィルム（太閤ＦＯＲ フタムラ ＃２０）に印刷して４０〜５０℃で乾燥し、次いでインラインにてイソプロピルアルコールを塗工、４０〜５０℃で乾燥し、ブリード痕の跡など外観を観察した。
◎ ：印刷物に外観不良の発生はなかった。
○ ：印刷物に若干むらが認められた。これ以上実用レベルである。
△ ：印刷物に薄くブリード痕が認められた。
× ：印刷物にはっきりブリード痕が認められた。
[Alcohol bleed resistance]
The white diluted printing ink 1 is printed on a corona-treated OPP film (Taiko FOR Futamura # 20) using a gravure proofing machine equipped with a 35 μm gravure printing plate, dried at 40-50 ° C., and then coated with isopropyl alcohol in-line. After drying at 40 to 50 ° C., the appearance such as bleed marks was observed.
A: There was no appearance defect on the printed matter.
○: Some unevenness was observed in the printed matter. More practical than that.
Δ: A thin bleed mark was observed on the printed matter.
X: Bleed marks were clearly observed on the printed matter.
［ＥＬラミネート強度］
版かぶり性試験の印刷条件で、片面コロナ処理で厚み２０μｍのポリプロピレン（以下ＯＰＰ）フィルム「パイレンＰ−２１６１（東洋紡績株式会社製）」、片面コロナ処理で厚み１２μｍのポリエチレンテレフタレート（以下ＰＥＴ）フィルム「東洋紡エステルフィルムＥ５１００（東洋紡績株式会社製）」を基材とした印刷物を得て、ポリエチレンイミン系アンカーコート剤「オリバインＥＬ−４２０」（東洋モートン株式会社製、商品名）を塗布し、塗布面上にシーラントとして低密度ポリエチレン「ノバテックＬＣ６００」（日本ポリケム株式会社製、商品名）の溶融温度を３１５℃にて押し出し、ラミネート加工物を得た。低密度ポリエチレンの溶融温度は、押し出しラミネート機のＴダイ直下における温度を接触式温度計（安立計器株式会社製ＨＬ−１００）にて測定した。該ラミネート加工物におけるインキ部を巾１５ｍｍで裁断し、インキ面と溶融樹脂層の層間で剥離させた後、剥離強度をインテスコ製２０１万能引張り試験機にて剥離強度の測定を行った。なお、ＯＰＰ／イミン構成では１．０Ｎ／１５ｍｍ以上、ＰＥＴ／イミン構成では１．５Ｎ／１５ｍｍ以上を実用レベルとする。
[EL laminate strength]
Polypropylene (hereinafter referred to as OPP) film “Pyrene P-2161 (manufactured by Toyobo Co., Ltd.)” having a thickness of 20 μm by single-sided corona treatment under the printing conditions of the plate fog test, and polyethylene terephthalate (hereinafter “PET”) film having a thickness of 12 μm by single-sided corona treatment A printed material based on “Toyobo Ester Film E5100 (Toyobo Co., Ltd.)” was obtained, and a polyethyleneimine anchor coating agent “Olivein EL-420” (trade name, manufactured by Toyo Morton Co., Ltd.) was applied and applied. The melt temperature of low density polyethylene “Novatech LC600” (trade name, manufactured by Nippon Polychem Co., Ltd.) as a sealant was extruded on the surface at 315 ° C. to obtain a laminated product. The melting temperature of the low density polyethylene was measured with a contact thermometer (HL-100, manufactured by Anritsu Keiki Co., Ltd.) as the temperature immediately below the T die of the extrusion laminating machine. The ink part in the laminated product was cut at a width of 15 mm and peeled between the ink surface and the molten resin layer, and the peel strength was measured with an Intesco 2.01 million tensile tester. Note that the practical level is 1.0 N / 15 mm or more for the OPP / imine configuration and 1.5 N / 15 mm or more for the PET / imine configuration.
評価結果を表３および表４にまとめる。実施例１〜１６の印刷インキは、比較例１〜８の印刷インキ組成物と比較し、エステル／アルコール溶剤系において優れた版かぶり性等の印刷適性を示し、かつ耐ブロッキング性、接着性、耐アルコールブリード性、さらにラミネート適性等の印刷物性を確保できる、印刷インキ組成物を提供することができる。 The evaluation results are summarized in Tables 3 and 4. The printing inks of Examples 1 to 16 show printability such as excellent plate fogging in an ester / alcohol solvent system as compared with the printing ink compositions of Comparative Examples 1 to 8, and have blocking resistance, adhesiveness, It is possible to provide a printing ink composition that can ensure printing property such as alcohol bleeding resistance and suitability for lamination.
Claims (3)
並びに混合溶剤を含むポリウレタン樹脂組成物であって、
下記の（Ａ）〜（Ｆ）であることを特徴とするポリウレタン樹脂組成物。
（Ａ）ポリイソシアネートの全イソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（全）］／［ＯＨ］が、１．８〜２．３である。
（Ｂ）トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が、１．０〜２．１である。
（Ｃ）ポリウレタン樹脂の水酸基価が１．０〜１０．０ｍｇＫＯＨ／ｇである。
（Ｄ）有機ジアミンのモル数ｄ１とアルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２が、３〜２５である。
（Ｅ）混合溶剤が、エステル系溶剤とアルコール系溶剤とを含む。
（Ｆ）高分子ポリオールが、ポリエステルジオールとポリエーテルジオールとからなる。 A polyurethane resin obtained by reacting a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol with an organic diamine and an alkanolamine,
A polyurethane resin composition comprising a mixed solvent,
A polyurethane resin composition comprising the following (A) to (F) .
(A) The molar ratio [NCO (total)] / [OH] in the reaction of all isocyanate groups of the polyisocyanate and hydroxyl groups of the polymer polyol is 1.8 to 2.3.
(B) The molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol is 1.0 to 2.1.
(C) The hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
(D) The molar ratio d1 / d2 between the number of moles d1 of the organic diamine and the number of moles d2 of the alkanolamine is 3-25.
(E) The mixed solvent includes an ester solvent and an alcohol solvent.
(F) The polymer polyol is composed of a polyester diol and a polyether diol.
高分子ポリオール中の、ポリエステルジオールが２０〜８０重量％、ポリエーテルジオール８０〜２０重量％であることを特徴とする請求項1記載のポリウレタン樹脂組成物。 The polymer polyol consists of polyester diol and polyether diol,
2. The polyurethane resin composition according to claim 1, wherein the polyester polyol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in the polymer polyol.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012115512A JP5130553B1 (en) | 2012-03-28 | 2012-05-21 | Polyurethane resin composition for printing ink binder |
| KR1020147029220A KR101588234B1 (en) | 2012-03-28 | 2013-03-19 | Polyurethane resin composition for printing ink binder |
| SG11201406055SA SG11201406055SA (en) | 2012-03-28 | 2013-03-19 | Polyurethane resin composition for printing ink binder |
| MYPI2014702779A MY169259A (en) | 2012-03-28 | 2013-03-19 | Polyurethane resin composition for printing ink binder |
| CN201380016733.8A CN104204020B (en) | 2012-03-28 | 2013-03-19 | Polyurethane for printing ink binder resin combination |
| PCT/JP2013/057772 WO2013146452A1 (en) | 2012-03-28 | 2013-03-19 | Polyurethane resin composition for printing ink binder |
| PH12014502125A PH12014502125B1 (en) | 2012-03-28 | 2014-09-24 | Polyurethane resin composition for printing ink binder |
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| JP2012115512A JP5130553B1 (en) | 2012-03-28 | 2012-05-21 | Polyurethane resin composition for printing ink binder |
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| JP2013227465A JP2013227465A (en) | 2013-11-07 |
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| KR (1) | KR101588234B1 (en) |
| CN (1) | CN104204020B (en) |
| MY (1) | MY169259A (en) |
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| JP6150133B2 (en) * | 2014-02-28 | 2017-06-21 | 東洋インキＳｃホールディングス株式会社 | Printing ink composition |
| JP5728749B1 (en) * | 2014-03-24 | 2015-06-03 | 東洋インキＳｃホールディングス株式会社 | Printing ink |
| JP6179775B2 (en) * | 2014-04-08 | 2017-08-16 | 東洋インキＳｃホールディングス株式会社 | PTP packaging ink composition and laminate |
| JP2016094548A (en) * | 2014-11-14 | 2016-05-26 | サカタインクス株式会社 | High solid ink composition for organic solvent gravure printing and gravure printing method |
| CN110546215B (en) * | 2017-05-16 | 2020-12-18 | Dic油墨株式会社 | Liquid ink composition, printed matter, and laminated laminate |
| JP6905130B1 (en) * | 2020-07-07 | 2021-07-21 | 大日精化工業株式会社 | Printing ink using biopolyurethane resin |
| CN112279989A (en) * | 2020-10-30 | 2021-01-29 | 南通高盟新材料有限公司 | Alcohol-soluble polyurethane ink binder and preparation method thereof |
| KR102570035B1 (en) * | 2023-01-31 | 2023-08-22 | 김병길 | Painting guide canvas colored with high-temperature color change ink composition and manufacturing method thereof |
| KR102565983B1 (en) * | 2023-04-04 | 2023-08-11 | 주식회사 풍림피앤피 | Eco-friendly ink composition for flexographic printing |
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| WO2009060838A1 (en) * | 2007-11-05 | 2009-05-14 | Asahi Glass Company, Limited | Polyurethane for printing ink binder, method for producing the same and printing ink |
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| JP3446477B2 (en) * | 1996-06-03 | 2003-09-16 | 東洋インキ製造株式会社 | Polyurethane resin for printing ink and printing ink using the same |
| JP3972666B2 (en) | 2002-01-30 | 2007-09-05 | 大日本インキ化学工業株式会社 | Binder for printing ink |
| JP2004175867A (en) * | 2002-11-26 | 2004-06-24 | Dainippon Ink & Chem Inc | Urethane urea resin composition for flexographic printing ink, flexographic printing ink and laminate film |
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| WO2009060838A1 (en) * | 2007-11-05 | 2009-05-14 | Asahi Glass Company, Limited | Polyurethane for printing ink binder, method for producing the same and printing ink |
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| SG11201406055SA (en) | 2014-11-27 |
| PH12014502125A1 (en) | 2014-12-10 |
| KR101588234B1 (en) | 2016-01-25 |
| MY169259A (en) | 2019-03-19 |
| CN104204020A (en) | 2014-12-10 |
| PH12014502125B1 (en) | 2014-12-10 |
| WO2013146452A1 (en) | 2013-10-03 |
| CN104204020B (en) | 2016-02-17 |
| JP2013227465A (en) | 2013-11-07 |
| KR20140139566A (en) | 2014-12-05 |
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