JP2017002184A - Polyurethane urea resin solution and printing ink - Google Patents
Polyurethane urea resin solution and printing ink Download PDFInfo
- Publication number
- JP2017002184A JP2017002184A JP2015117613A JP2015117613A JP2017002184A JP 2017002184 A JP2017002184 A JP 2017002184A JP 2015117613 A JP2015117613 A JP 2015117613A JP 2015117613 A JP2015117613 A JP 2015117613A JP 2017002184 A JP2017002184 A JP 2017002184A
- Authority
- JP
- Japan
- Prior art keywords
- urea resin
- polyurethane urea
- parts
- resin solution
- printing ink
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 103
- 239000011347 resin Substances 0.000 title claims abstract description 103
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 88
- 238000007639 printing Methods 0.000 title claims abstract description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 125000003277 amino group Chemical group 0.000 claims abstract description 43
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 62
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 8
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 68
- 239000000976 ink Substances 0.000 description 52
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 35
- 150000002009 diols Chemical class 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- -1 Aliphatic glycols Chemical class 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- 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 10
- 229920005906 polyester polyol Polymers 0.000 description 10
- 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 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000001361 adipic acid Substances 0.000 description 9
- 235000011037 adipic acid Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 125000005442 diisocyanate group Chemical group 0.000 description 9
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000004658 ketimines Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 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
- 239000012298 atmosphere Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 230000036962 time dependent Effects 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-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
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-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
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- 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
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- XXNPWUCSMZUOOC-UHFFFAOYSA-N 2-butyl-2-ethylpentanedioic acid Chemical compound CCCCC(CC)(C(O)=O)CCC(O)=O XXNPWUCSMZUOOC-UHFFFAOYSA-N 0.000 description 1
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 239000005062 Polybutadiene Substances 0.000 description 1
- 229930183415 Suberin Natural products 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、印刷インキ用のバインダーとして有用なポリウレタンウレア樹脂溶液、及びそれを用いた印刷インキに関する。 The present invention relates to a polyurethane urea resin solution useful as a binder for printing ink and a printing ink using the same.
ポリエステル系のポリウレタンウレア樹脂溶液を印刷インキ用のバインダーとして用いた印刷インキは、優れた顔料分散性を有するとともに、各種プラスチック製の基材に対して優れた接着性能を示す点で有用である。また、近年、環境問題に対応する観点から、臭気等が問題視されているトルエンやメチルエチルケトン（ＭＥＫ）を含有しない印刷インキが用いられている。具体的には、エステル系溶剤やアルコール系溶剤を主体とした、いわゆるノントルエンノンＭＥＫ印刷インキが用いられている。 A printing ink using a polyester-based polyurethane urea resin solution as a binder for printing ink is useful in that it has excellent pigment dispersibility and exhibits excellent adhesion performance to various plastic substrates. In recent years, printing inks that do not contain toluene or methyl ethyl ketone (MEK), which are considered problematic in terms of odor, have been used from the viewpoint of addressing environmental problems. Specifically, a so-called non-toluene non-MEK printing ink mainly composed of an ester solvent or an alcohol solvent is used.
印刷インキ用のバインダーに用いるポリエステル系のポリウレタンウレア樹脂としては、顔料分散性及び各種プラスチック製の基材に対する接着性能の観点から、末端に活性アミノ基を有するポリウレタンウレア樹脂が有用である。しかし、末端に活性アミノ基を有するポリウレタンウレア樹脂と、エステル系溶剤やアルコール系溶剤を主体とする有機溶剤とを含有する溶液は、経時的に粘度が低下しやすいといった課題があった。また、この溶液は、それに含まれるポリウレタンウレア樹脂の分子量が低下しやすく、さらには樹脂の物性も変化しやすいという課題があった。そして、この溶液をバインダーとして用いた印刷インキも経時的に粘度が低下するとともに、印刷適性が変化しやすいという課題があった。 As the polyester-based polyurethane urea resin used as a binder for printing ink, a polyurethane urea resin having an active amino group at the terminal is useful from the viewpoint of pigment dispersibility and adhesion performance to various plastic substrates. However, a solution containing a polyurethane urea resin having an active amino group at the terminal and an organic solvent mainly composed of an ester solvent or an alcohol solvent has a problem that the viscosity tends to decrease with time. In addition, this solution has a problem that the molecular weight of the polyurethane urea resin contained in the solution tends to decrease, and the physical properties of the resin also easily change. And the printing ink which used this solution as a binder also had the subject that a printability changed easily while a viscosity fell with time.
末端に活性アミノ基を有するポリウレタンウレア樹脂と、エステル系溶剤やアルコール系溶剤を主体とする有機溶剤とを含有する溶液の経時的な粘度低下を防止すべく、例えば、ヒドロキシカルボン酸を配合したバインダー等が提案されている（特許文献１及び２）。 In order to prevent a decrease in viscosity over time of a solution containing a polyurethane urea resin having an active amino group at the terminal and an organic solvent mainly composed of an ester solvent or an alcohol solvent, for example, a binder containing a hydroxycarboxylic acid Etc. have been proposed (Patent Documents 1 and 2).
しかし、本発明者らの検討の結果、特許文献１及び２で提案されたバインダー等を用いて形成した被膜は、湿熱条件下で劣化しやすいことが判明した。また、上記のバインダー等を配合した印刷インキを用いて形成したインキ被膜についても、バインダー等を用いて形成した被膜と同様に、湿熱条件下で劣化しやすいことが分かった。 However, as a result of the study by the present inventors, it has been found that the film formed using the binder proposed in Patent Documents 1 and 2 is likely to deteriorate under wet heat conditions. In addition, it was found that an ink film formed using a printing ink containing the above-described binder or the like is likely to deteriorate under wet heat conditions, similarly to a film formed using a binder or the like.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、臭気が低減されているとともに、粘度安定性に優れており、かつ、湿熱条件下であっても強度等の物性が劣化しにくい耐湿熱性に優れた被膜を形成することが可能な、印刷インキ用のバインダーとして有用なポリウレタンウレア樹脂溶液を提供することにある。また、本発明の課題とするところは、上記のポリウレタンウレア樹脂溶液をバインダーとして用いた印刷インキを提供することにある。 The present invention has been made in view of such problems of the prior art, and the problem is that the odor is reduced, the viscosity stability is excellent, and the heat and humidity conditions are satisfied. However, it is an object of the present invention to provide a polyurethane urea resin solution useful as a binder for printing inks, which can form a film excellent in moisture and heat resistance in which physical properties such as strength are not easily deteriorated. Moreover, the place made into the subject of this invention is providing the printing ink which used said polyurethane urea resin solution as a binder.
すなわち、本発明によれば、以下に示すポリウレタンウレア樹脂溶液が提供される。
［１］末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂、エステル系溶剤、アルコール系溶剤、及びアセトンを含有し、前記アセトンの含有量が、前記活性アミノ基の量に対して、０．１〜１０モル当量であるポリウレタンウレア樹脂溶液。
［２］前記エステル系溶剤が酢酸エチルであり、前記アルコール系溶剤がイソプロピルアルコールである前記［１］に記載のポリウレタンウレア樹脂溶液。
［３］前記ポリウレタンウレア樹脂の固形分１ｇ当たりの前記活性アミノ基の量が、１５〜１００μｇ当量である前記［１］又は［２］に記載のポリウレタンウレア樹脂溶液。
That is, according to the present invention, the following polyurethane urea resin solution is provided.
[1] A polyester-based polyurethane urea resin having an active amino group at the terminal, an ester solvent, an alcohol solvent, and acetone. The content of the acetone is 0. 0 relative to the amount of the active amino group. A polyurethane urea resin solution having 1 to 10 molar equivalents.
[2] The polyurethane urea resin solution according to [1], wherein the ester solvent is ethyl acetate and the alcohol solvent is isopropyl alcohol.
[3] The polyurethane urea resin solution according to [1] or [2], wherein the amount of the active amino group per 1 g of the solid content of the polyurethane urea resin is 15 to 100 μg equivalent.
また、本発明によれば、以下に示す印刷インキが提供される。
［４］印刷インキ用のバインダー及び顔料を含有する印刷インキであって、前記バインダーが、前記［１］〜［３］のいずれかに記載のポリウレタンウレア樹脂溶液である印刷インキ。
Moreover, according to this invention, the printing ink shown below is provided.
[4] A printing ink containing a binder for printing ink and a pigment, wherein the binder is the polyurethane urea resin solution according to any one of [1] to [3].
本発明によれば、臭気が低減されているとともに、粘度安定性に優れており、かつ、湿熱条件下であっても強度等の物性が劣化しにくい耐湿熱性に優れた被膜を形成することが可能な、印刷インキ用のバインダーとして有用なポリウレタンウレア樹脂溶液を提供することができる。また、本発明によれば、上記のポリウレタンウレア樹脂溶液をバインダーとして用いた印刷インキを提供することができる。 According to the present invention, it is possible to form a film that has reduced odor, is excellent in viscosity stability, and has excellent moisture and heat resistance, such that the physical properties such as strength are not easily deteriorated even under wet heat conditions. A possible polyurethane urea resin solution useful as a binder for printing inks can be provided. Moreover, according to this invention, the printing ink which used said polyurethane urea resin solution as a binder can be provided.
＜ポリウレタンウレア樹脂溶液＞
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。
<Polyurethane urea resin solution>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.
本発明のポリウレタンウレア樹脂溶液は、末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂、エステル系溶剤、アルコール系溶剤、及びアセトンを含有する。そして、ポリウレタンウレア樹脂溶液中のアセトンの含有量は、ポリウレタンウレア樹脂の活性アミノ基の量に対して、０．１〜１０モル当量である。以下、その詳細について説明する。 The polyurethane urea resin solution of the present invention contains a polyester polyurethane urea resin having an active amino group at the terminal, an ester solvent, an alcohol solvent, and acetone. And content of acetone in a polyurethane urea resin solution is 0.1-10 molar equivalent with respect to the quantity of the active amino group of a polyurethane urea resin. The details will be described below.
末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂と、エステル系溶剤やアルコール系溶剤を主体とする有機溶剤とを含有する溶液の粘度が経時的に低下する理由を、本発明者らは以下のように推測している。すなわち、活性アミノ基によって、ポリウレタンウレア樹脂のアルコール系溶剤によるエステル交換分解が促進される。そして、樹脂溶液中に存在する微量の水分によって、ポリウレタンウレア樹脂の加水分解がさらに促進されると考えられる。 The reason why the viscosity of a solution containing a polyester-based polyurethane urea resin having an active amino group at the terminal and an organic solvent mainly composed of an ester solvent or an alcohol solvent decreases with time is as follows. I guess that. That is, the transesterification decomposition of the polyurethane urea resin by the alcohol solvent is promoted by the active amino group. And it is thought that hydrolysis of a polyurethane urea resin is further accelerated | stimulated by the trace amount water | moisture content which exists in a resin solution.
本発明者らは、ポリウレタンウレア樹脂の活性アミノ基の量に対して上記所定の割合となるようにアセトンを配合することで、湿熱条件下においてもポリウレタンウレア樹脂が劣化しにくくなること見出した。また、トルエンやＭＥＫなどの有機溶剤を実質的に含有させることなく、アセトンを含有させることで、臭気を低減することもできる。すなわち、アセトンは、末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂を含有する溶液の粘度を安定化させる粘度安定化剤として機能する成分であると考えられる。 The present inventors have found that the polyurethane urea resin is less likely to be deteriorated even under wet heat conditions by blending acetone so as to have the above predetermined ratio with respect to the amount of active amino groups of the polyurethane urea resin. Moreover, an odor can also be reduced by containing acetone, without substantially containing organic solvents, such as toluene and MEK. That is, acetone is considered to be a component that functions as a viscosity stabilizer that stabilizes the viscosity of a solution containing a polyester-based polyurethane urea resin having an active amino group at the terminal.
活性アミノ基の量に対して上記所定の割合となるようにアセトンを配合することで、ケチミン化反応によって活性アミノ基がアセトンによりマスクされる。これにより、樹脂の分解による経時的な粘度低下が抑制されると推測される。なお、上記のケチミン化反応は可逆的であるため、アセトンは印刷インキの乾燥時に他の溶剤とともに飛散する。このため、アセトンの配合量が上記の範囲内である本発明のポリウレタンウレア樹脂溶液、及びこれを用いた印刷インキは、臭気の面においても優れている。 By blending acetone so as to have the above-mentioned predetermined ratio with respect to the amount of the active amino group, the active amino group is masked with acetone by the ketimination reaction. Thereby, it is presumed that the decrease in viscosity over time due to the decomposition of the resin is suppressed. In addition, since said ketimination reaction is reversible, acetone scatters with another solvent at the time of drying of printing ink. For this reason, the polyurethane urea resin solution of the present invention in which the blending amount of acetone is within the above range, and the printing ink using the same are excellent in terms of odor.
従来市販の印刷インキに多く使用されるＭＥＫと比較して、アセトンは同じケトン系溶剤であっても人体に対する影響の程度が低い。さらに、アセトンは、有害大気汚染物質（ＨＡＰＳ）規制に代表される大気汚染物質にも指定されていない。このため、ＭＥＫに代えてアセトンを含有する本発明のポリウレタンウレア樹脂溶液は、環境に対する負荷も低減されている。 Compared with MEK, which is conventionally used in many commercially available printing inks, acetone has a lower influence on the human body even if it is the same ketone solvent. Furthermore, acetone is not designated as an air pollutant represented by the Hazardous Air Pollutant (HAPS) regulations. For this reason, the polyurethane urea resin solution of the present invention containing acetone instead of MEK has a reduced burden on the environment.
（ポリウレタンウレア樹脂）
ポリウレタンウレア樹脂は、末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂であって、印刷インキ用のバインダーに用いられるものであれば、いずれの樹脂であってもよい。なお、本明細書における「活性アミノ基」とは、活性水素を有する一級アミノ基及び二級アミノ基を意味する。上記のようなポリウレタンウレア樹脂は、例えば、以下に示すように製造することができる。まず、ポリエステルポリオールを含む高分子ジオールと有機ジイソシアネートを反応させて両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得る。次いで、得られたウレタンプレポリマーのイソシアネート基に対して過剰量のジアミンを作用させ、鎖伸長反応させることによって、末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂を得ることができる。
(Polyurethane urea resin)
The polyurethane urea resin may be any resin as long as it is a polyester-based polyurethane urea resin having an active amino group at the terminal and is used as a binder for printing ink. In the present specification, the “active amino group” means a primary amino group and a secondary amino group having active hydrogen. The polyurethane urea resin as described above can be produced, for example, as shown below. First, a polymer diol containing a polyester polyol is reacted with an organic diisocyanate to obtain a urethane prepolymer having isocyanate groups at both ends. Next, an excess amount of diamine is allowed to act on the isocyanate group of the obtained urethane prepolymer to cause a chain extension reaction, whereby a polyester-based polyurethane urea resin having an active amino group at the terminal can be obtained.
ポリエステルポリオールとしては、多価カルボン酸と多価アルコールを重縮合して得られるポリエステルポリオールを用いることができる。多価カルボン酸の具体例としては、コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、酒石酸、シュウ酸、マロン酸、ピメリン酸、スベリン酸、グルタコン酸、アゼライン酸、１，４−シクロヘキシルジカルボン酸、α−ハイドロムコン酸、β−ハイドロムコン酸、α−ブチル−α−エチルグルタル酸、α，β−ジエチルサクシン酸などの二塩基酸；及びこれらの無水物を挙げることができる。 As the polyester polyol, a polyester polyol obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol can be used. Specific examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, tartaric acid, oxalic acid, malonic acid, pimelic acid, and suberin. Dibasic acids such as acid, glutaconic acid, azelaic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid And anhydrides thereof.
多価アルコールの具体例としては、エチレングリコール、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、トリプロピレングリコール、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、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、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、ネオペンチルグリコールなどの脂肪族グリコール；ビスヒドロキシメチルシクロヘキサン、シクロヘキサン−１，４−ジオールなどの脂環族グリコール；キシリレングリコールなどの芳香族グリコール；炭素数１〜１８のアルキルジエタノールアミンなどのアルキルジアルカノールアミンなどのグリコール類を挙げることができる。 Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8 Aliphatic glycols such as octanediol, 1,9-nonanediol, neopentyl glycol; alicyclic glycols such as bishydroxymethylcyclohexane and cyclohexane-1,4-diol; aromatic glycols such as xylylene glycol; carbon number 1-18 alkyldiethanos Glycols such as alkyl dialkanolamines, such as amine.
ポリエステルポリオールの具体例としては、ポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリ２−メチル−１，３−プロパンジオールアジペート、ポリ３−メチル−１，５−ペンタンジオールアジペート、ポリネオペンチルグリコールアジペートなどの縮合系ポリエステルポリオール；上記のジオール類などを開始剤として使用し、ラクトンを開環重合させて得られるポリラクトンジオール、ポリカプロラクトンジオール、ポリメチルバレロラクトンジオールなどのラクトン系ポリエステルジオールを挙げることができる。 Specific examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, poly-2-methyl-1,3-propanediol adipate, poly-3-methyl-1,5-pentanediol adipate, polyneopentyl glycol Condensed polyester polyols such as adipate; lactone polyester diols such as polylactone diols, polycaprolactone diols and polymethylvalerolactone diols obtained by ring-opening polymerization of lactones using the above diols as initiators be able to.
ポリエステルポリオールの数平均分子量は、５００〜６，０００であることが好ましい。ポリエステルポリオールの数平均分子量が５００未満であると、得られるポリウレタンウレア樹脂の溶剤への再溶解性が乏しくなる場合があり、印刷インキの高速印刷適性が低下することがある。一方、ポリエステルポリオールの数平均分子量が６，０００超であると、得られるポリウレタンウレア樹脂の耐熱性が乏しくなる場合があり、印刷インキに要求される巻取り時の耐ブロッキング性が低下することがある。 The number average molecular weight of the polyester polyol is preferably 500 to 6,000. If the number average molecular weight of the polyester polyol is less than 500, the re-solubility of the resulting polyurethane urea resin in the solvent may be poor, and the high-speed printability of the printing ink may be reduced. On the other hand, if the number average molecular weight of the polyester polyol is more than 6,000, the resulting polyurethane urea resin may have poor heat resistance, and the blocking resistance during winding required for printing ink may be reduced. is there.
ポリエステルポリオール以外の高分子ジオールとして、例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシテトラブチレングリコール、ポリカーボネートジオール、ポリブタジエンジオールなどをポリエステルポリオールと併用してもよい。 As polymer diols other than polyester polyol, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxytetrabutylene glycol, polycarbonate diol, polybutadiene diol and the like may be used in combination with polyester polyol. .
有機ジイソシアネートの具体例としては、ヘキサメチレンジイソシアネート、ブタン−１，４−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、２，４，４−トリメチルヘキサメチレンジイソシアネート、キシリレンジイソシアネート、ｍ−テトラメチルキシリレンジイソシアネートなどの脂肪族ジイソシアネート；イソホロ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、リジンジイソシアネート、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、４，４’−ジシクロヘキシルメタンジイソシアネート、イソプロピリデンジシクロヘキシル−４，４’−ジイソシアネート、ノルボルナンジイソシアネートなどの脂環族ジイソシアネート；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’−ジベンジルジイソシアネート、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、水素添加キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネートなどの芳香族ジイソシアネートを挙げることができる。 Specific examples of the organic diisocyanate include hexamethylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl. Aliphatic diisocyanates such as xylylene diisocyanate; isophorone diisocyanate, cyclohexane-1,4-diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, norvo Alicyclic diisocyanates such as nadiisocyanate; 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyl Mention may be made of aromatic diisocyanates such as diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate.
上記の有機ジイソシアネートの他、例えば、上記有機ジイソシアネートのビューレット変性体、アロファネート変性体、イソシアヌレート変性体、カルボジイミド変性体等の変性体；上記有機ジイソシアネートとポリオールを反応させて得られるアダクト体などを用いることもできる。反応性や物性などの総合的な観点から、有機ジイソシアネートとしては、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、ト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が好ましい。これらの有機ジイソシアネートは、１種単独で又は２種以上を組み合わせて用いることができる。 In addition to the above organic diisocyanates, for example, modified products such as burette modified products, allophanate modified products, isocyanurate modified products, and carbodiimide modified products of the above organic diisocyanates; adducts obtained by reacting the above organic diisocyanates with polyols, etc. It can also be used. From the comprehensive viewpoints such as reactivity and physical properties, the organic diisocyanate is preferably isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, or 4,4'-diphenylmethane diisocyanate. These organic diisocyanates can be used alone or in combination of two or more.
ジアミンとしては、脂肪族ジアミン、脂環族ジアミン、及び芳香族ジアミンを用いることができる。ジアミンの具体例としては、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、イソホロンジアミン、シクロヘキシルジアミン、ピペラジン、２−メチルピペラジン、フェニレンジアミン、トリレンジアミン、キシレンジアミン、１，３−シクロヘキシルジアミン、４，４’−ジアミノジシクロヘキシルアミン、ｍ−キシリレンジアミン、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、ジ−２−ヒドロキシプロピルエチレンジアミン、これらの水素添加物、及びこれらの混合物などを挙げることができる。 Aliphatic diamine, alicyclic diamine, and aromatic diamine can be used as the diamine. Specific examples of the diamine include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, isophoronediamine, cyclohexyldiamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, 1,3-cyclohexyldiamine, 4 , 4'-diaminodicyclohexylamine, m-xylylenediamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylpropylenediamine, di-2-hydroxypropylethylenediamine, hydrogenated products thereof, And a mixture thereof.
また、必要に応じて、ジアミンとともに、モノアミン類を反応停止剤として用いることができる。モノアミン類の具体例としては、モノ−ｎ−ブチルアミン、ジ−ｎ−ブチルアミン、モノエタノールアミン、ジエタノールアミンなどを挙げることができる。 Moreover, monoamines can be used as a reaction terminator with diamine as needed. Specific examples of monoamines include mono-n-butylamine, di-n-butylamine, monoethanolamine, diethanolamine and the like.
ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は、１５〜１００μｇ当量であることが好ましい。活性アミノ基の量がポリウレタンウレア樹脂の固形分１ｇ当たり１５μｇ当量未満であると、ポリプロピレンフィルムやポリエステルフィルムに対する密着性が低下する場合がある。一方、活性アミノ基の量がポリウレタンウレア樹脂の固形分１ｇ当たり１００μｇ当量超であると、例えば、イソシアネート硬化剤を配合した二液インキ使用時での配合液の粘度上昇が激しくなることで、可使時間が短縮される場合がある。なお、ポリウレタンウレア樹脂の末端の活性アミノ基の量は、例えば、ウレタンプレポリマー、鎖伸長剤としてのジアミン類、及び反応停止剤としてのモノアミン類の配合比を調整することによって制御することができる。 The amount of active amino groups per gram of solid content of the polyurethane urea resin is preferably 15 to 100 μg equivalent. When the amount of the active amino group is less than 15 μg equivalent per 1 g of the solid content of the polyurethane urea resin, the adhesion to the polypropylene film or the polyester film may be lowered. On the other hand, if the amount of active amino groups exceeds 100 μg equivalent per gram of solid content of the polyurethane urea resin, for example, the increase in viscosity of the blended liquid when using a two-component ink blended with an isocyanate curing agent becomes significant. Usage time may be shortened. The amount of the active amino group at the end of the polyurethane urea resin can be controlled, for example, by adjusting the blending ratio of the urethane prepolymer, the diamine as a chain extender, and the monoamine as a reaction terminator. .
（有機溶剤）
本発明のポリウレタンウレア樹脂溶液は、有機溶剤として、エステル系溶剤、アルコール系溶剤、及びアセトンを含有する。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ｎ−ブチル、酢酸イソブチルなどを挙げることができる。なかでも、酢酸エチルが好ましい。ポリウレタンウレア樹脂溶液中のエステル系溶剤の含有量については特に限定されないが、通常、２０〜９５質量％であればよい。
(Organic solvent)
The polyurethane urea resin solution of the present invention contains an ester solvent, an alcohol solvent, and acetone as an organic solvent. Examples of the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate. Of these, ethyl acetate is preferred. The content of the ester solvent in the polyurethane urea resin solution is not particularly limited, but may be usually 20 to 95% by mass.
アルコール系溶剤としては、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、ターシャリーブチルアルコールなどを挙げることができる。なかでも、イソプロピルアルコールが好ましい。ポリウレタンウレア樹脂溶液中のアルコール系溶剤の含有量については特に限定されないが、通常、５〜６０質量％であればよい。 Examples of alcohol solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, and tertiary butyl alcohol. Of these, isopropyl alcohol is preferred. The content of the alcohol-based solvent in the polyurethane urea resin solution is not particularly limited, but may be usually 5 to 60% by mass.
本発明のポリウレタンウレア樹脂溶液を調製する方法は特に限定されない。例えば、末端に活性アミノ基を有するポリエステル系のポリウレタンウレア樹脂と、エステル系溶剤及びアルコール系溶剤とを含有する樹脂溶液を調製した後、活性アミノ基の量に対して所定の割合となるようにアセトンを添加して混合することで、本発明のポリウレタンウレア樹脂溶液を得ることができる。 The method for preparing the polyurethane urea resin solution of the present invention is not particularly limited. For example, after preparing a resin solution containing a polyester-based polyurethane urea resin having an active amino group at the terminal, an ester solvent and an alcohol solvent, the ratio is set to a predetermined ratio with respect to the amount of active amino groups. The polyurethane urea resin solution of the present invention can be obtained by adding and mixing acetone.
＜印刷インキ＞
本発明の印刷インキは、印刷インキ用のバインダー及び顔料を含有する。そして、印刷インキ用のバインダーが、前述のポリウレタンウレア樹脂溶液である。
<Printing ink>
The printing ink of the present invention contains a binder and a pigment for printing ink. And the binder for printing ink is the above-mentioned polyurethane urea resin solution.
本発明の印刷インキに用いる顔料の種類は特に限定されない。例えば、従来公知の無機顔料及び有機顔料のいずれであっても用いることができる。なお、印刷インキ中の顔料の含有量については特に限定されないが、通常、５〜５０質量％であればよい。 The kind of pigment used for the printing ink of the present invention is not particularly limited. For example, any of conventionally known inorganic pigments and organic pigments can be used. In addition, although it does not specifically limit about content of the pigment in printing ink, Usually, what is necessary is just 5-50 mass%.
本発明の印刷インキを調製する方法は特に限定されない。例えば、まず、ポリウレタンウレア樹脂溶液、顔料、及びエステル系溶剤やアルコール系溶剤などの希釈用有機溶剤を混合するとともに、必要に応じて、分散剤、ブロッキング防止剤、消泡剤、レベリング剤、カップリング剤、可塑剤、乾燥制御のための遅乾性溶剤、及び紫外線吸収剤、酸化防止剤などを添加する。次いで、公知の各種分散機を使用して分散させれば、本発明の印刷インキを得ることができる。 The method for preparing the printing ink of the present invention is not particularly limited. For example, first, a polyurethane urea resin solution, a pigment, and an organic solvent for dilution such as an ester solvent or an alcohol solvent are mixed, and if necessary, a dispersant, an antiblocking agent, an antifoaming agent, a leveling agent, a cup A ring agent, a plasticizer, a slow-drying solvent for controlling drying, an ultraviolet absorber, an antioxidant and the like are added. Subsequently, if it disperse | distributes using a well-known various disperser, the printing ink of this invention can be obtained.
本発明の印刷インキ中のバインダーの含有量については特に限定されないが、ポリウレタンウレア樹脂溶液（但し、固形分として）の含有量は、通常、１０〜５０質量％であればよい。また、本発明の印刷インキには、本発明の効果を損なわない範囲で、必要に応じて、硝化綿、塩素化ポリエチレン、塩素化ポリプロピレン、塩化ビニル−酢酸ビニル共重合樹脂、マレイン酸樹脂、ポリビニルブチラール樹脂、繊維素系樹脂などを含有させることもできる。 The content of the binder in the printing ink of the present invention is not particularly limited, but the content of the polyurethane urea resin solution (however, as a solid content) may be usually 10 to 50% by mass. In addition, the printing ink of the present invention includes, as necessary, nitrified cotton, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyvinyl as long as the effects of the present invention are not impaired. Butyral resins, fiber-based resins, and the like can also be included.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.
＜ポリウレタンウレア樹脂溶液（バインダー）の調製＞
（実施例１）
アジピン酸と、ネオペンチルグリコール／１，４−ブタンジオール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６６．５部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２３．５部、酢酸エチル９８１．２部、及びイソプロピルアルコール２０６．５部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５５．４部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン０．２９部（樹脂末端の活性アミノ基の量に対して０．２モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１０２０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４２．７μｇ当量であった。
<Preparation of polyurethane urea resin solution (binder)>
Example 1
A polyester diol having a number average molecular weight of 3,000, which was obtained using adipic acid and neopentyl glycol / 1,4-butanediol = 7/3 (molar ratio), was prepared. 500 parts of this polyester diol and 66.5 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 23.5 parts of isophoronediamine, 981.2 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 755.4 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 0.29 parts of acetone (0.2 molar equivalent with respect to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1020 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 42.7 μg equivalent.
（実施例２）
アジピン酸と、ネオペンチルグリコール／１，４−ブタンジオール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６６．５部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２３．５部、酢酸エチル９６８．３部、及びイソプロピルアルコール２０６．５部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５５．４部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン１３．１部（樹脂末端の活性アミノ基の量に対して９モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１０１０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４２．７μｇ当量であった。
(Example 2)
A polyester diol having a number average molecular weight of 3,000, which was obtained using adipic acid and neopentyl glycol / 1,4-butanediol = 7/3 (molar ratio), was prepared. 500 parts of this polyester diol and 66.5 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 23.5 parts of isophoronediamine, 968.3 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 755.4 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 13.1 parts of acetone (9 molar equivalents relative to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1010 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 42.7 μg equivalent.
（実施例３）
アジピン酸と、３−メチル−１，５−ペンタンジオール／１，４−ブタンジオール＝８／２（モル比）とを用いて得られた、数平均分子量２，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート８８．６部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率２．０３％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１９６．２部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２５．４部、ジ−ｎ−ブチルアミン１．８部、酢酸エチル１０２３．７部、及びイソプロピルアルコール２１５．６部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７８５．０部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン１．７部（樹脂末端の活性アミノ基の量に対して１モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１２００ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４６．１μｇ当量であった。
(Example 3)
A polyester diol having a number average molecular weight of 2,000, obtained by using adipic acid and 3-methyl-1,5-pentanediol / 1,4-butanediol = 8/2 (molar ratio) was prepared. 500 parts of this polyester diol and 88.6 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 2.03%. The obtained urethane prepolymer was dissolved in 196.2 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 25.4 parts of isophoronediamine, 1.8 parts of di-n-butylamine, 1023.7 parts of ethyl acetate, and 215.6 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 785.0 parts of a urethane prepolymer solution was added dropwise and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 1.7 parts of acetone (1 molar equivalent with respect to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1200 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 46.1 μg equivalent.
（実施例４）
アジピン酸と、２−メチル−１，３−ブタンジオール／エチレングリコール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６２．８部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．６７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８７．６部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２０．３部、ジ−ｎ−ブチルアミン０．８６部、酢酸エチル９６９．４部、及びイソプロピルアルコール２０４．４部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５０．５部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン１．３部（樹脂末端の活性アミノ基の量に対して１モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１３００ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は３８．２μｇ当量であった。
Example 4
A polyester diol having a number average molecular weight of 3,000, obtained by using adipic acid and 2-methyl-1,3-butanediol / ethylene glycol = 7/3 (molar ratio) was prepared. 500 parts of this polyester diol and 62.8 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was performed at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.67%. The obtained urethane prepolymer was dissolved in 187.6 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 20.3 parts of isophoronediamine, 0.86 parts of di-n-butylamine, 969.4 parts of ethyl acetate, and 204.4 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 750.5 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 1.3 parts of acetone (1 molar equivalent with respect to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1300 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 38.2 μg equivalent.
（比較例１）
アジピン酸と、ネオペンチルグリコール／１，４−ブタンジオール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６６．５部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２３．５部、酢酸エチル９８１．５部、及びイソプロピルアルコール２０６．５部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５５．４部を滴下し、４０℃で１時間反応させた。これにより、不揮発分３０％、粘度１０２０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４２．７μｇ当量であった。
(Comparative Example 1)
A polyester diol having a number average molecular weight of 3,000, which was obtained using adipic acid and neopentyl glycol / 1,4-butanediol = 7/3 (molar ratio), was prepared. 500 parts of this polyester diol and 66.5 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 23.5 parts of isophoronediamine, 981.5 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 755.4 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1020 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 42.7 μg equivalent.
（比較例２）
アジピン酸と、ネオペンチルグリコール／１，４−ブタンジオール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６６．５部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２３．５部、酢酸エチル９８１．４部、及びイソプロピルアルコール２０６．５部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５５．４部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン０．０７３部（樹脂末端の活性アミノ基の量に対して０．０５モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１０２０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４２．７μｇ当量であった。
(Comparative Example 2)
A polyester diol having a number average molecular weight of 3,000, which was obtained using adipic acid and neopentyl glycol / 1,4-butanediol = 7/3 (molar ratio), was prepared. 500 parts of this polyester diol and 66.5 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 23.5 parts of isophoronediamine, 981.4 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 755.4 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 0.073 parts of acetone (0.05 molar equivalent with respect to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1020 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 42.7 μg equivalent.
（比較例３）
アジピン酸と、ネオペンチルグリコール／１，４−ブタンジオール＝７／３（モル比）とを用いて得られた、数平均分子量３，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート６６．５部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率１．８７％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１８８．８部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２３．５部、酢酸エチル９５２．２部、及びイソプロピルアルコール２０６．５部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７５５．４部を滴下し、４０℃で１時間反応させた。粘度安定剤としてアセトン２９．３部（樹脂末端の活性アミノ基の量に対して２０モル当量）を添加し、４０℃で３０分ケチミン化反応させた。これにより、不揮発分３０％、粘度１０１０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４２．７μｇ当量であった。
(Comparative Example 3)
A polyester diol having a number average molecular weight of 3,000, which was obtained using adipic acid and neopentyl glycol / 1,4-butanediol = 7/3 (molar ratio), was prepared. 500 parts of this polyester diol and 66.5 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 23.5 parts of isophoronediamine, 952.2 parts of ethyl acetate, and 206.5 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 755.4 parts of a urethane prepolymer solution was dropped and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 29.3 parts of acetone (20 molar equivalents relative to the amount of active amino groups at the end of the resin) was added, and a ketimine reaction was performed at 40 ° C. for 30 minutes. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1010 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 42.7 μg equivalent.
（比較例４）
アジピン酸と、３−メチル−１，５−ペンタンジオール／１，４−ブタンジオール＝８／２（モル比）とを用いて得られた、数平均分子量２，０００のポリエステルジオールを用意した。このポリエステルジオール５００部、及びイソホロンジイソシアネート８８．６部を反応容器に入れた。窒素気流下、１００℃で５時間反応させて、ＮＣＯ基含有率２．０３％のウレタンプレポリマーを得た。得られたウレタンプレポリマーを酢酸エチル１９６．２部に溶解して、不揮発分７５％のウレタンプレポリマー溶液を得た。イソホロンジアミン２５．４部、ジ−ｎ−ブチルアミン１．８部、酢酸エチル１０２６．２部、及びイソプロピルアルコール２１５．６部を別の反応容器に入れた。内容物を撹拌しながらウレタンプレポリマー溶液７８５．０部を滴下し、４０℃で１時間反応させた。粘度安定剤として酒石酸２．１部（樹脂末端の活性アミノ基の量に対して１モル当量）を添加した。これにより、不揮発分３０％、粘度１１８０ｍＰａ・ｓ（２５℃）のポリウレタンウレア樹脂溶液を得た。ポリウレタンウレア樹脂の固形分１ｇ当たりの活性アミノ基の量は４６．１μｇ当量であった。
(Comparative Example 4)
A polyester diol having a number average molecular weight of 2,000, obtained by using adipic acid and 3-methyl-1,5-pentanediol / 1,4-butanediol = 8/2 (molar ratio) was prepared. 500 parts of this polyester diol and 88.6 parts of isophorone diisocyanate were placed in a reaction vessel. The reaction was carried out at 100 ° C. for 5 hours under a nitrogen stream to obtain a urethane prepolymer having an NCO group content of 2.03%. The obtained urethane prepolymer was dissolved in 196.2 parts of ethyl acetate to obtain a urethane prepolymer solution having a nonvolatile content of 75%. 25.4 parts of isophoronediamine, 1.8 parts of di-n-butylamine, 1026.2 parts of ethyl acetate, and 215.6 parts of isopropyl alcohol were placed in a separate reaction vessel. While stirring the contents, 785.0 parts of a urethane prepolymer solution was added dropwise and reacted at 40 ° C. for 1 hour. As a viscosity stabilizer, 2.1 parts of tartaric acid (1 molar equivalent relative to the amount of active amino groups at the resin terminal) was added. As a result, a polyurethane urea resin solution having a nonvolatile content of 30% and a viscosity of 1180 mPa · s (25 ° C.) was obtained. The amount of active amino groups per gram of solid content of the polyurethane urea resin was 46.1 μg equivalent.
＜ポリウレタンウレア樹脂溶液の評価＞
（１）経時粘度安定性
ポリウレタンウレア樹脂溶液を４０℃で１カ月間保管した。ポリウレタンウレア樹脂溶液の保管前後の２５℃における粘度を測定し、粘度保持率（％）を算出した。そして、以下に示す評価基準にしたがって経時粘度安定性を評価した。結果を表１に示す。
［評価基準］
○：粘度保持率９５％以上
△：粘度保持率８０％以上９５％未満
×：粘度保持率８０％未満
<Evaluation of polyurethane urea resin solution>
(1) Viscosity stability over time The polyurethane urea resin solution was stored at 40 ° C. for 1 month. The viscosity at 25 ° C. before and after storage of the polyurethane urea resin solution was measured, and the viscosity retention rate (%) was calculated. And the time-dependent viscosity stability was evaluated according to the evaluation criteria shown below. The results are shown in Table 1.
[Evaluation criteria]
○: Viscosity retention 95% or more Δ: Viscosity retention 80% or more and less than 95% ×: Viscosity retention 80% or less
（２）臭気
ポリウレタンウレア樹脂溶液を４０μｍスリットのコーターにてＰＥＴフィルムに塗布した。そして、比較例１のポリウレタンウレア樹脂溶液（アセトン無添加）を対照品とし、以下に示す評価基準にしたがって官能的に臭気を評価した。結果を表１に示す。
［評価基準］
○：対照品と比較して大差なし
△：対照品と比較して刺激臭が感じられる
×：対照品と比較して刺激臭が強い
(2) Odor Polyurethane urea resin solution was applied to a PET film with a 40 μm slit coater. Then, the polyurethane urea resin solution (without addition of acetone) of Comparative Example 1 was used as a control product, and the odor was sensoryly evaluated according to the following evaluation criteria. The results are shown in Table 1.
[Evaluation criteria]
○: No significant difference compared to the control product △: Stimulating odor is felt compared to the control product ×: Strong odor compared to the control product
（３）耐湿熱性
ポリウレタンウレア樹脂溶液を離型紙上に塗布した後、乾燥して、厚さ５０μｍの被膜が形成されたフィルムを作製した。作製したフィルムを７０℃、９５％ＲＨの雰囲気中に２週間放置した。引張試験機を使用し、２００ｍｍ／ｍｉｎの引張速度で放置前後のフィルムの破断強度を測定し、破断強度保持率（％）を算出した。そして、以下に示す評価基準にしたがって耐湿熱性を評価した。結果を表１に示す。
［評価基準］
○：破断強度保持率８０％以上
△：破断強度保持率６０％以上８０％未満
×：破断強度保持率６０％未満
(3) Moisture and heat resistance After the polyurethane urea resin solution was applied onto the release paper, it was dried to produce a film on which a film having a thickness of 50 μm was formed. The produced film was left in an atmosphere of 70 ° C. and 95% RH for 2 weeks. Using a tensile tester, the breaking strength of the film before and after standing was measured at a tensile speed of 200 mm / min, and the breaking strength retention rate (%) was calculated. And the heat-and-moisture resistance was evaluated according to the evaluation criteria shown below. The results are shown in Table 1.
[Evaluation criteria]
○: Breaking strength retention 80% or more Δ: Breaking strength retention 60% or more and less than 80% ×: Breaking strength retention 60% or less
＜印刷インキの調製＞
（実施例５）
酸化チタン白３５部、実施例１のポリウレタンウレア樹脂溶液４０部、酢酸ｎ−プロピル１０部、及びイソプロピルアルコール１５部を混合及び混練して白インキを得た。得られた白インキに酢酸エチル／イソプロピルアルコールの混合溶剤（質量比＝５０／５０）を添加して＃３ザーンカップ１８秒に粘度を調整し、印刷インキを得た。
<Preparation of printing ink>
(Example 5)
White ink was obtained by mixing and kneading 35 parts of titanium oxide white, 40 parts of the polyurethane urea resin solution of Example 1, 10 parts of n-propyl acetate, and 15 parts of isopropyl alcohol. A mixed solvent of ethyl acetate / isopropyl alcohol (mass ratio = 50/50) was added to the obtained white ink to adjust the viscosity at # 3 Zahn cup for 18 seconds to obtain a printing ink.
（実施例６〜８及び比較例５〜８）
実施例１のポリウレタンウレア樹脂溶液に代えて、実施例２〜４及び比較例１〜４のポリウレタンウレア樹脂溶液をそれぞれ用いたこと以外は、前述の実施例５と同様にして各印刷インキを得た。
(Examples 6-8 and Comparative Examples 5-8)
Each printing ink was obtained in the same manner as in Example 5 except that the polyurethane urea resin solutions of Examples 2 to 4 and Comparative Examples 1 to 4 were used in place of the polyurethane urea resin solution of Example 1. It was.
＜印刷インキの評価＞
（１）経時粘度安定性
印刷インキを４０℃で１カ月間保管した。印刷インキの保管前後の２５℃における粘度を測定し、粘度保持率（％）を算出した。そして、以下に示す評価基準にしたがって経時粘度安定性を評価した。結果を表２に示す。
［評価基準］
○：粘度保持率９５％以上
△：粘度保持率８０％以上９５％未満
×：粘度保持率８０％未満
<Evaluation of printing ink>
(1) Viscosity stability with time The printing ink was stored at 40 ° C. for 1 month. The viscosity at 25 ° C. before and after storing the printing ink was measured, and the viscosity retention rate (%) was calculated. And the time-dependent viscosity stability was evaluated according to the evaluation criteria shown below. The results are shown in Table 2.
[Evaluation criteria]
○: Viscosity retention 95% or more Δ: Viscosity retention 80% or more and less than 95% ×: Viscosity retention 80% or less
（２）臭気
印刷インキを４０μｍスリットのコーターにて厚さ１００μｍのＰＥＴフィルムに塗布した。そして、比較例５の印刷インキ（アセトン無添加）を対照品とし、以下に示す評価基準にしたがって官能的に臭気を評価した。結果を表１に示す。
［評価基準］
○：対照品と比較して大差なし
△：対照品と比較して刺激臭が感じられる
×：対照品と比較して刺激臭が強い
(2) Odor Printing ink was applied to a PET film having a thickness of 100 μm using a coater having a 40 μm slit. Then, the printing ink of Comparative Example 5 (without addition of acetone) was used as a control, and the odor was evaluated sensorily according to the following evaluation criteria. The results are shown in Table 1.
[Evaluation criteria]
○: No significant difference compared to the control product △: Stimulating odor is felt compared to the control product ×: Strong odor compared to the control product
（３）耐湿熱性
版深３５μｍのグラビア版を装着したグラビア印刷機を用意した。この印刷機を使用し、コロナ放電処理された厚さ１２μｍの二軸延伸ＰＥＴフィルムに印刷インキを２回重ねて印刷した後、５０℃で乾燥して白印刷フィルムを得た。得られた白印刷フィルムを１日放置した後、７０℃、９５％ＲＨの雰囲気中に２週間暴露する湿熱試験を行った。さらに、湿熱試験前後の白印刷フィルムについて、以下に示す密着性試験を行った。そして、セロファンテープを引き剥がした後の印刷面の状態を目視で観察し、以下に示す評価基準にしたがって耐湿熱性を評価した。結果を表２に示す。
［密着性試験］
セロファンテープ（商品名「セロテープ（登録商標） ２４ｍｍ」、ニチバン社製）を白印刷フィルムの印刷面に貼り付けた後、角度９０度で一気に引き剥がした。
［評価基準］
○：湿熱試験後の密着性試験で、ＰＥＴフィルムに残ったインキの量（インキ残量）が９０％以上であった。
△：湿熱試験後の密着性試験で、ＰＥＴフィルムに残ったインキの量（インキ残量）が５０％以上９０％未満であった。
×：湿熱試験後の密着性試験で、ＰＥＴフィルムに残ったインキの量（インキ残量）が５０％未満であった。
(3) Moisture and heat resistance A gravure printing machine equipped with a gravure plate having a plate depth of 35 μm was prepared. Using this printer, printing ink was applied twice to a 12 μm thick biaxially stretched PET film subjected to corona discharge treatment, and then dried at 50 ° C. to obtain a white printing film. The obtained white printing film was allowed to stand for 1 day, and then a wet heat test was performed in which it was exposed to an atmosphere of 70 ° C. and 95% RH for 2 weeks. Furthermore, the adhesiveness test shown below was done about the white printing film before and behind the wet heat test. And the state of the printing surface after peeling off a cellophane tape was observed visually, and the heat-and-moisture resistance was evaluated according to the evaluation criteria shown below. The results are shown in Table 2.
[Adhesion test]
Cellophane tape (trade name “Cello Tape (registered trademark) 24 mm”, manufactured by Nichiban Co., Ltd.) was attached to the printing surface of the white printing film, and then peeled off at an angle of 90 degrees.
[Evaluation criteria]
○: In the adhesion test after the wet heat test, the amount of ink remaining on the PET film (remaining ink amount) was 90% or more.
Δ: In the adhesion test after the wet heat test, the amount of ink remaining on the PET film (remaining ink amount) was 50% or more and less than 90%.
X: In the adhesion test after the wet heat test, the amount of ink remaining on the PET film (remaining ink amount) was less than 50%.
本発明のポリウレタンウレア樹脂溶液は、印刷インキ用のバインダーとして有用である。 The polyurethane urea resin solution of the present invention is useful as a binder for printing ink.
Claims (4)
前記アセトンの含有量が、前記活性アミノ基の量に対して、０．１〜１０モル当量であるポリウレタンウレア樹脂溶液。 Containing a polyester-based polyurethane urea resin having an active amino group at the end, an ester-based solvent, an alcohol-based solvent, and acetone;
The polyurethane urea resin solution whose content of the said acetone is 0.1-10 molar equivalent with respect to the quantity of the said active amino group.
前記アルコール系溶剤がイソプロピルアルコールである請求項１に記載のポリウレタンウレア樹脂溶液。 The ester solvent is ethyl acetate,
The polyurethane urea resin solution according to claim 1, wherein the alcohol solvent is isopropyl alcohol.
前記バインダーが、請求項１〜３のいずれか一項に記載のポリウレタンウレア樹脂溶液である印刷インキ。 A printing ink containing a binder and a pigment for printing ink,
Printing ink whose said binder is the polyurethane urea resin solution as described in any one of Claims 1-3.
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