JP4345335B2 - Water-based polyurethane resin and printing ink using the resin - Google Patents
Water-based polyurethane resin and printing ink using the resin Download PDFInfo
- Publication number
- JP4345335B2 JP4345335B2 JP2003093228A JP2003093228A JP4345335B2 JP 4345335 B2 JP4345335 B2 JP 4345335B2 JP 2003093228 A JP2003093228 A JP 2003093228A JP 2003093228 A JP2003093228 A JP 2003093228A JP 4345335 B2 JP4345335 B2 JP 4345335B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin
- water
- acid
- polyurethane resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims description 53
- 238000007639 printing Methods 0.000 title claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 59
- 229920005989 resin Polymers 0.000 title description 48
- 239000011347 resin Substances 0.000 title description 48
- 238000004519 manufacturing process Methods 0.000 claims description 66
- 239000004593 Epoxy Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000002924 oxiranes Chemical class 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 78
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000000034 method Methods 0.000 description 29
- 239000000976 ink Substances 0.000 description 20
- -1 xylene Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011362 coarse particle Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 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 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000000539 dimer Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000000466 oxiranyl group Chemical group 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-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
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- BMASLOOHTMQIGP-ZOKJKDLISA-H (z)-but-2-enedioate;butyltin(3+) Chemical compound CCCC[Sn+3].CCCC[Sn+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O BMASLOOHTMQIGP-ZOKJKDLISA-H 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-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
- 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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- FGPFIXISGWXSCE-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)propane-1,3-diol Chemical compound C1OC1COCC(CO)(CO)COCC1CO1 FGPFIXISGWXSCE-UHFFFAOYSA-N 0.000 description 1
- SKWCZPYWFRTSDD-UHFFFAOYSA-N 2,3-bis(azaniumyl)propanoate;chloride Chemical compound Cl.NCC(N)C(O)=O SKWCZPYWFRTSDD-UHFFFAOYSA-N 0.000 description 1
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- OFKACPUBCORWTG-UHFFFAOYSA-N 2,5-bis(oxiran-2-yl)oxolane Chemical compound C1OC1C1OC(C2OC2)CC1 OFKACPUBCORWTG-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 1
- LDOMKUVUXZRECL-UHFFFAOYSA-N 2-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=C(C(O)=O)C=CC=C1C(O)=O LDOMKUVUXZRECL-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YTNUOGWCFLMGLF-UHFFFAOYSA-N 5-methylbenzene-1,2,3,4-tetrol Chemical compound CC1=CC(O)=C(O)C(O)=C1O YTNUOGWCFLMGLF-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001800 Shellac Polymers 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YVHDRFKHKGNLNW-UHFFFAOYSA-L [dibutyl(octadecanoyloxy)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCCCCCCCC YVHDRFKHKGNLNW-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- BWIFZLKAOGSBOD-UHFFFAOYSA-M acetyloxy(butyl)tin Chemical compound CCCC[Sn]OC(C)=O BWIFZLKAOGSBOD-UHFFFAOYSA-M 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 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
- 229940058302 antinematodal agent piperazine and derivative Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- DIVTWACHZOQOBF-UHFFFAOYSA-K diacetyloxy(butyl)stannanylium;acetate Chemical compound CCCC[Sn](OC(C)=O)(OC(C)=O)OC(C)=O DIVTWACHZOQOBF-UHFFFAOYSA-K 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、ポリウレタン樹脂を水性媒体中でエポキシ化合物により鎖延長して得られる水性ポリウレタン樹脂及び、それを使用した水性インキに関する。本発明のエポキシ化合物により鎖延長して得られた水性ポリウレタン樹脂は、プラスチックフィルム、プラスチックシートへの濡れ性、接着性、ラミネート性能に優れ、インキ、塗料、接着剤、特に水性印刷インキ分野に有用である。
【０００２】
【従来の技術】
従来、ポリウレタンはその優れた機械的性質、耐摩耗性、耐薬品性、接着性などの特性を活かして、ゴムとプラスチックスの境界分野を埋める樹脂として、塗料、接着剤、人工皮革などの幅広い用途分野に浸透している。その中で、環境保全、省資源、安全性といった社会ニーズに対応すべく、水性ポリウレタンが急激に発展してきている。ウレタン樹脂の水中への乳化分散技術、アイオノマー化による自己乳化分散技術、さらには水中での高分子量化技術等に進歩により高性能の水性ポリウレタンが出現し、その性能は今日では溶剤系ポリウレタン樹脂に匹敵するレベルになり、各種の用途分野で実用化されるに至っている。
【０００３】
しかしながら、水性ポリウレタンの問題点として、水性化する場合に必要な乳化剤やイオン基により、ポリウレタン樹脂本来の特性、例えば、耐溶剤性や耐熱性を阻害することがしばしばある。
【０００４】
一般的に、水性ポリウレタン樹脂は、その製造方法から強制乳化法、ケトン法、プレポリマー水中攪拌法、溶融分散方法、ケチミン法、自己乳化方法が知られている。水性インキに用いられるウレタン樹脂は、顔料分散性、印刷適性、フィルムへの接着性、耐水性などから、一般的にケトン法、すなわちイソシアネート基を含むプレポリマーをケトン系溶媒などの有機溶剤等で合成し中和後、脱溶剤過程を経てエマルジョン、コロイダルデスパージョン、水溶解型等の水性ウレタン樹脂が使用されてきた。
【０００５】
ケトン法により製造するポリウレタン樹脂は、水性ポリウレタン樹脂とするため脱溶剤工程を必要とする。この脱溶剤工程に要する時間、コスト、有機溶剤の再利用、焼却廃棄等を軽減するため、例えば特開昭５９−１３８２１１号公報にはアクリルモノマー中でポリウレタン合成し、複合化させる方法が開示されている。この方法では、一般に活性水素を有しない不飽和単量体を必要としており、活性水素を有する通常の不飽和単量体を使用するとイソシアネ−トと不飽和単量体との反応が起こることからウレタン樹脂の分子量を伸ばすことが困難になる欠点があった。また、この方法では、鎖延長反応において著しく粘度上昇することからウレタン樹脂の濃度を下げることや、あるいは特殊な撹拌装置を必要とするなどの欠点もあった。
【０００６】
かかる問題に対し、例えば、特開平６−３０６１３５号公報で末端イソシアネート基を有するウレタンプレポリマーを水に乳化分散した後ポリアミンで鎖延長し、得られたエマルジョンを架橋剤としてエポキシ樹脂を使用することが開示されている。しかしながら、この方法では使用する乳化剤のため充分な接着性、耐水性、ラミネート物性が得られない。特開平５−２９５０７６号公報ではイソシアネート末端プレポリマーを水中で乳化し、アミン基末端エポキシ樹脂で鎖延長する方法が開示されている。この方法では、乳化剤の悪影響が避けられない。
【０００７】
特開２０００−１０９６８１号公報では、水性ポリウレタン樹脂の製造時に使用する乳化剤よる性能低下を改善するため、エポキシ基を有する化合物とアミノ基を持つポリビニルアルコールを使用することを開示している。この方法ではある程度の耐溶剤性は得られるが、接着性は不十分であった。
【０００８】
特開平１１−２７９２３６号公報には有機溶媒として水酸基をもつアクリルモノマー中でポリウレタン樹脂を合成し、水中に分散後他のアクリルモノマーを重合するする方法が開示されている。この方法は脱溶媒工程を省く上で有効であるが、アクリル樹脂が全てポリウレタン樹脂に複合化されないため、フィルムへの接着性やラミネート強度は不十分であった。
エポキシ樹脂の接着性やポリウレタン樹脂の接着性、機械的性質に着眼し、エポキシ樹脂を用いた水性ポリウレタン樹脂も検討されている。
【０００９】
【特許文献１】
特開昭５９−１３８２１１号公報
【特許文献２】
特開平６−３０６１３５号公報
【特許文献３】
特開平５−２９５０７６号公報
【特許文献４】
特開２０００−１０９６８１号公報
【特許文献５】
特開平１１−２７９２３６号公報
【００１０】
【発明が解決しようとする課題】
本発明は、水性ポリウレタン樹脂の製造において水転相時に乳化剤を含まず、かつプラスチックフィルムへの濡れ性、接着性、ラミネート適性に優れた水性ポリウレタン樹脂を提供することを目的とする。
【００１１】
【課題を解決するための手段】
本発明は、ポリウレタン樹脂を水系媒体中でエポキシ化合物により鎖延長を行うことにより、脱有機溶剤工程の低減と、優れた顔料分散性、印刷物の外観品質（印刷効果）を有し、かつ基材への接着性などの諸特性が良好な水性ポリウレタン樹脂が得られること、更には水性ポリウレタン樹脂は印刷インキに極めて有用であることを見出し、本発明に至った。
【００１２】
即ち、本発明は、ポリウレタン樹脂の水分散体／水可溶体を得た後、エポキシ化合物を添加し該ポリウレタン樹脂中のカルボキシル基と反応させる水性ポリウレタン樹脂の製造方法において、エポキシ化合物が分子内に少なくとも２個以上のオキシラン環を有し、ポリウレタン樹脂（固形分）１００重量部当たり、エポキシ化合物を０．３〜２０重量部の範囲で添加、反応させる、重量平均分子量が２００００〜１５０００００であり、酸価が０．５〜７０である水性ポリウレタン樹脂の製造方法により得られる水性ポリウレタン樹脂を含有することを特徴とする印刷インキに関する。
【００１３】
以下、本発明の水性ポリウレタン樹脂液の製造方法を説明する。
本発明に用いられるポリウレタンプレポリマーは、実質的に、高分子ポリオール、有機ジイソシアネートおよび必要に応じて鎖伸長剤を、溶媒の存在下または不存在下で反応させて得られた、分子中にイソシアネート基を１個以上有するポリウレタンである。
【００１４】
（ウレタン製造方法）
ポリウレタンプレポリマーの製造は、従来から公知の方法で行うことができ、３０〜１５０℃の温度条件下で、有機溶媒の存在下または不存在下で行うことができる。この際用いることができる有機溶媒としては、アセトン、メチルエチルケトン等のケトン類；テトラヒドロフラン、ジオキサン等のエーテル類；酢酸エチル、酢酸ブチル等のエステル類；ジメチルホルムアミド、Ｎ−メチルピロリドン等のアミド類；トルエン、キシレン等の芳香族炭化水素等が挙げられ、エマルジョン製造後の溶媒除去の容易性を考慮すると、アセトン、メチルエチルケトン、酢酸エチル等の沸点が１００℃未満の溶媒がより好ましい。また、プレポリマー製造後に、粘度低下等を目的として、上記の有機溶媒を添加、あるいは追加しても良い。
【００１５】
ポリウレタンプレポリマーの製造に用いうる高分子ポリオールとしては、ポリエステルポリオール、ポリカーボネートポリオール、ポリエステルポリカーボネートポリオール、ポリエーテルポリオールなどを挙げることができ、ポリウレタンプレポリマーはこれらの高分子ポリオールの１種または２種以上を用いて形成されることができる。
【００１６】
(ジオール)
ジオールとして、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、1,2-プロパンジオール、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、1,6-ヘキサンジオール、オクタンジオール、1,4-ブチレンジオール、ジプロピレングリコールなどの低分子ジオール類を用いることができる。また、酸化エチレン、酸化プロピレン、テトラヒドロフラン等の重合体もしくは共重合体等のポリエーテルポリオール類；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、1,2-プロパンジオール、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、1,6-ヘキサンジオール、オクタンジオール、1,4-ブチレンジオール、ジプロピレングリコールなどの飽和または不飽和の低分子ジオール類またはn-ブチルグリシジルエーテル、2-エチルヘキシルグリシジルエーテルなどのアルキルグリシジルエーテル類、バーサティック酸グリシジルエステルなどのモノカルボン酸グリシジルエステル類と、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、スベリン酸、アゼライン酸、セバシン酸などのジカルボン酸類あるいはこれらの無水物やダイマー酸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を開環重合して得られるポリカプロラクトンジオールなどのポリエステルポリオール類；低分子ジオールとカーボネイトとを反応させて得られるポリ−カーボネートポリオール類；ポリブタジエングリコール類；ビスフェノールＡ、ビスフェノールＦ、水添ビスフェノールＡに酸化エチレンまたは酸化プロピレンを付加させて得られるグリコール類など、ポリウレタン樹脂の製造に通常用いられる高分子ポリオールを例示することができる。
【００１７】
（イソシアネート種類）
有機ジイソシアネートとしては、芳香族、脂肪族または脂環族の各種公知のジイソシアネート類を使用することができる。例えば、1,5-ナフチレンジイソシアネート、4,4'−ジフェニルメタンジイソシアネート、4,4'−ジフェニルジメチルメタンジイソシアネート、4,4'−ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、1,3-フェニレンジイソシアネート、1,4-フェニレンジイソシアネート、トリレンジイソシアネート、ブタン−1,4-ジイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、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、m-テトラメチルキシリレ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を例示することができる。
【００１８】
（酸基種類）
酸基を付与する成分として、例えば、２，２−ジメチロールプロピオン酸、２，２−ジメチロール酪酸、２，２−ジメチロール吉草酸等のジメチロールアルカン酸；グルタミン、アスパラギン、リジン、ジアミノプロピオン酸、オルニチン、ジアミノ安息香酸、ジアミノベンゼンスルホン酸等のジアミン型アミノ酸類；(A-3) グリシン、アラニン、グルタミン酸、タウリン、アスパラギン酸、アミノ酪酸、バリン、アミノカプロン酸、アミノ安息香酸、アミノイソフタル酸、スルファミン酸などのモノアミン型アミノ酸類を例示することができる。好ましくは、２，２−ジメチロールプロピオン酸、２，２−ジメチロール酪酸である。
【００１９】
（ウレア基鎖延長）
本発明で使用するポリウレタン樹脂骨格は、エポキシ化合物による反応に先立ち、通常のポリウレタン樹脂に使用されるウレア反応により鎖延長することが出来る。ウレア基の導入はイソシアネート基末端ポリウレタン樹脂中のイソシアネート基が０．１重量％以上にすることが、エポキシ化合物による鎖延長を効果的にする。ウレア基鎖伸長剤成分としては、通常のポリウレタン樹脂の製造に従来から用いられている鎖伸長剤のいずれもが使用できるが、イソシアネート基と反応し得る活性水素原子を分子中に２個以上有する分子量３００以下の低分子ジアミン化合物を用いるのが好ましい。例えば、ジヒドラジン、エチレンジアミン、プロピレンジアミン、キシリレンジアミン、イソホロンジアミン、ピペラジンおよびその誘導体、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、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジドなどのジアミン類； これらのうち１種または２種以上を用いることができる。
【００２０】
（ポリウレタン樹脂の重合溶媒について）
本発明で用いられるイソシアネートに対して不活性でかつ親水性の有機溶剤としては、例えばテトラヒドロフラン、ジオキサン等のエーテル類、酢酸エチル等のエステル類、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、ジメチルホルムアミド、Ｎ−メチルピロリドン等のアミド類等が挙げられるが、ポリウレタンの水性化後は通常減圧蒸留により除去されるため、また、脱溶剤しないで使用する場合でも乾燥速度を早めるため、好ましくは水より低沸点の溶剤の使用が望ましい。
【００２１】
(ポリウレタン樹脂の分子量)
高分子ポリオール成分の数平均分子量は５００〜１００００であることが必要である。数平均分子量が５００〜１００００の範囲から外れる高分子ポリオールを用いて製造されたポリウレタンプレポリマーを使用する場合は、得られるポリウレタン組成物の耐寒性、耐熱性、耐溶剤性などが低下したものとなりやすい。
【００２２】
(ウレタン化触媒)
ポリウレタンプレポリマーの製造の際には、必要に応じて反応触媒を添加することができ、このような触媒としては例えば、オクチル酸スズ、モノブチルスズトリアセテート、モノブチルスズモノオクチレート、モノブチルスズモノアセテート、モノブチルスズマレイン酸塩、ジブチルスズジアセテート、ジブチルスズジオクトエート、ジブチルスズジステアレート、ジブチルスズジラウレート、ジブチルスズマレイン酸塩などの有機スズ化合物；テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネートなどの有機チタン化合物；トリエチルアミン、Ｎ，Ｎ−ジエチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、トリエチレンジアミンなどの３級アミンなどを挙げることができる。
【００２３】
（水の添加方法）
ポリウレタン樹脂を水分散化する方法としては、該プレポリマー溶液を攪拌しながら水を滴下させて転相乳化させても良いし、或は良く攪拌している水中へプレポリマー溶液を滴下させてもよい。或はホモゲナイザ−、コロイドミル等による機械的なせんだん力を与えながら水分散化する方法は好ましい方法である。又、水分散化に際して超音波を使用する方法も好ましいものである。
【００２４】
（中和剤の種類）
本発明で用いられるポリウレタン樹脂の酸基を中和する塩基性物質としては、アンモニア；モノエチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、メチルジエタノールアミン、モノエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モルホリン、Ｎ−メチルモルホリン、2-アミノ−2-メチル−1-プロパノール等の有機アミン類；水酸化ナトリウム、水酸化カリウム等の無機アルカリ類等が挙げられ、１種または２種以上を組み合わせて用いられるが、乾燥後の皮膜の耐水性を向上させるためには、水溶性であり、かつ熱によって容易に解離する揮発性の高いものが好ましく、特にアンモニア、トリメチルアミン、トリエチルアミンが好ましい。
【００２５】
(中和剤の添加方法)
イソシアネート末端ポリウレタン樹脂は樹脂中に存在する酸成分の一部または全部を中和するためのアンモニアまたは揮発性アミンと共に水中に分散せしめるのであるが、その方法としてアルカリを含有する水を撹拌しつつ徐々にこの樹脂溶液を添加して分散溶解させるという方法によっても良いし、逆にこの樹脂溶液アルカリを含有する水を徐々に添加して分散溶解させる方法によっても良い。中和剤は、ポリウレタン樹脂に水を添加すると同時、もしくは水添加後に配合することが出来るが、水添加後が好ましい。更には、水添加に際しては、水の同時に少量のメタノール、エタノール、プロピルアルコールなどの共溶剤が使用できる。
【００２６】
（有機溶媒の除去）
本発明のポリウレタン樹脂製造は溶媒存在下、非存在下で行われるが、有機溶剤は水性媒体への転相後、あるいはエポキシ化合物により鎖伸長反応後、膜による方法、もしくは常圧、減圧での蒸留で除去できる。
【００２７】
かくして得られたポリウレタン樹脂に、分子内に少なくとも２個以上のオキシラン環を有するエポキシ化合物を添加し、ポリウレタン樹脂中のカルボキシル基、ヒドロキシル基、酸無水物のいづれかもしくは２種以上とオキシラン環が開環重合により鎖伸長される。
【００２８】
添加量
エポキシ化合物に含まれるエポキシ基が、ポリウレタン樹脂１００重量部（固形分）当り０．３から２０重量部（固形分）の範囲で添加、反応させる。０．５重量部を下回ると接着性、耐水性、耐油性が不十分である。２０重量部を越えるとコスト高になるばかりか、粘度上昇や低固形分化を生じる。
【００２９】
(エポキシ反応条件)
ポリウレタン樹脂にエポキシ化合物を添加する際の温度は、エポキシ化合物の副反応を避けるため５０〜９０℃が好ましい。
【００３０】
(エポキシ化合物)
本発明で使用するエポキシ化合物はモノアルキルアルコールもしくは多価アルキルアルコールのポリグリシジルエーテルからなる樹脂である。これらのエポキシ化合物のエポキシ当量は好ましくは１００〜２０００、特に好ましくは１００〜１０００である。
【００３１】
エポキシ化合物としては、分子内に１又は２個以上のオキシシラン環を有する樹脂である。オキシシラン環を分子内に２個以上有する化合物としては、ビスフェノールＡジグリシジルエーテル、ビスフェノールＡジβメチルグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、テトラヒドロキシフェニルメタンテトラグリシジルエーテル、レゾルシノールジグリシジルエーテル、ブロム化ビスフェノールＡジグリシジルエーテル、クロル化ビスフェノールＡジグリシジルエーテル、水素添加ビスフェノールＡジグリシジルエーテル、ビスフェノールＡアルキレンオキサイド付加物のジグリシジルエーテル、ノボラックグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、ペンタエリスリトールジグリシジルエーテル、エポキシウレタン樹脂等のグリシジルエーテル型；Ｐ−オキシ安息香酸グリシジルエーテル・エステル等のグリシジルエーテル・エステル型；フタル酸ジグリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル酸ジグリシジルエステル、アクリル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステル等のグリシジルエステル型；グリシジルアニリン、テトラグリシジルジアミノジフェニルメタン、トリグリシジルイソシアヌレート、トリグリシジルアミノフェノール等のグリシジルアミン型；エポキシ化ポリブタジエン、エポキシ化大豆油等の線状脂肪族エポキシ化合物；３,４エポキシ−６メチルシクロヘキシルメチル−３,４エポキシ−６メチルシクロヘキサンカルボキシレート、３,４−エポキシシクロヘキシルメチル（３,４−エポキシシクロヘキサン）カルボキシレート、ビス（３,４−エポキシ−６メチルシクロヘキシルメチル）アジペート、ビニルシクロヘキセンジエポキサイド、ジシクロペンタジエンオキサイド、ビス（２,３−エポキシシクロペンチル）エーテル、リモネンジオキサイド等の脂環族エポキシ化合物などが挙げられる。
【００３２】
なかでも、水溶性エポキシ化合物が好ましく、一例としては、ソルビトールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリチリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、トリグリシデルトリス（２−ヒドロキシエチル）イソシアヌレート、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグルシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１,６ヘキサンジオールジグリシジルエーテル、エチレン／プロピレングリコールジグリシジルエーテル等各種のものが挙げられる。
【００３３】
ウレタンと他種樹脂との反応
また、カルボキシル基、ヒドロキシル基、酸無水物のいづれかもしくは２種以上の反応基もつポリウレタン以外の水性・水分散性樹脂を、
エポキシ化合物を介してポリウレタン樹脂と反応させることが出来る。
反応基を持つ水性もしくは水分散樹脂としては、アクリル樹脂、ポリオレフィン樹脂、ポリビニルアルコール、ポリエステルポリオール、ポリカーボネートポリオール、ポリエステルポリカーボネートポリオール、ポリエーテルポリオール等各種のものが挙げられる。
【００３４】
分子量
上記水性ポリウレタン樹脂を印刷インキ用途として用いる場合、重量平均分子量は好ましくは２００００〜１５０００００、より好ましくは３００００〜５０００００の範囲である。２００００を下回ると、耐ブロッキング性、耐水性、ラミネート適性が低下する。１５０００００を上回ると顔料分散性、再溶解性が低下する。
【００３５】
酸価
同様に酸価は好ましくは０．５〜７０、より好ましくは２０〜５０の範囲である。０．５を下回るとインキの安定性が低下し７０を上回ると、耐水性、ラミネート適性が低下する。
【００３６】
本発明の水性印刷インキには、上記水性ポリウレタン樹脂の他、必要に応じてシェラック、ロジン変性マレイン酸樹脂、水性アクリル系樹脂、水性ポリエステル樹脂、既存の水性ポリウレタン樹脂などの水性樹脂を本発明の目的を妨げない範囲で配合できる。さらに水性印刷インキとしての必要な特性を付与するため、顔料などの着色剤、体質顔料、ワックス類、消泡剤、増粘剤、硬化剤、水および水混和性有機溶剤などが必要に応じて適宜添加され、アトライター、サンドミルなどの練肉機を使用して分散を行ない、所定の粘度になる様調整を行って水性印刷インキが製造される。かくして得られた水性印刷インキは、印刷時に適性粘度になるまで水または水混和性有機溶剤、例えばエチルアルコール、イソプロピルアルコール、ノルマルプロピルアルコールなどのアルコール系有機溶剤を混合した溶剤を用いて希釈し、グラビア印刷またはフレキソ印刷方式でプラスチックフィルムなどに印刷される。
【００３７】
本発明方法により得られるポリウレタン水性分散液は，フィルムや金属表面に対する接着性に優れ，且つ優れた耐水性、機械的性質を有している。印刷インキ分野では優れた印刷適性とラミネート適性が得られる。またスプレ−塗装やロ−ルコ−テイング等を用いて塗装され良好な塗膜を得ることが出来る。また特に金属等無機物に対する塗装性に優れ，従来のポリウレタン水性樹脂液では適用することが出来なかった多くの用途に供することができる。自動車塗料用や家庭塗料用ビヒクルをはじめガラスプラスチック、織物，紙，皮革，木材，金属の被覆，繊維及び織物への薄膜コ−テイング，毛皮用の表面コ−テイング，各種接着剤等広範囲の用途に使用することが出来る。
【実施例】
次に本発明を実施例により更に説明する。本実施例中の部及び％は特に断りのない限り重量基準である。
【００３８】
製造例１Ａ（プレポリマーの製造）
温度計、撹拌装置、還流冷却管を備えた４つ口フラスコに分子量２０００のポリテトラメチレングリコール１８４．８部、ジメチロールブタン酸２０部を加え高真空下１００℃、２０分間加熱を行い、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート４５．３部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万５千、酸価は３０であった。次に、温度を維持しながら水６４４．３部、２８％アンモニア水５．８部、イソプロピルアルコール１００部を加えこれを水溶化した。
【００３９】
製造例１Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４００部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。固形分２５％、ｐＨ７．６、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−１)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００４０】
製造例２Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリテトラメチレングリコール３３２．６部、ジメチロールブタン酸３６部、メチルエチルケトン１８０部を加え高真空下１００℃でメチルエチルケトン９０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート８１．５部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万、酸価は３０であった。次に、温度を維持しながら水１３３９．７部、２８％アンモニア水１０．４部を加えこれを水溶化した。
【００４１】
製造例２Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−2)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００４２】
製造例３Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、
分子量１８００の共重合ポリテトラメチレンエーテルグリコール（旭化成株式会社ＰＴＸＧ１８００）１８３部、ジメチロールブタン酸２０部メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート４７部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万、酸価は３０であった。次に、温度を維持しながら水７４４．３部、２８％アンモニア水５．８部を加えこれを水溶化した。
【００４３】
製造例３Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１２０万、酸価２７の樹脂溶液(ａ−3)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００４４】
製造例４Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリプロピレンアジペート１８４．８部、ジメチロールブタン酸２０部メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート４５．３部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万、酸価は３０であった。次に、温度を維持しながら水７４４．３部、２８％アンモニア水５．８部を加えこれを水溶化した。
【００４５】
製造例４Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−4)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００４６】
製造例５Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリテトラメチレングリコール１８０部、分子量４００のポリエチレングリコール３．５部、ジメチロールブタン酸２０部メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート４６．５部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は３万４千、酸価は３０であった。次に、温度を維持しながら水７４４．３部、２８％アンモニア水５．８部を加えこれを水溶化した。
【００４７】
製造例５Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１０万、酸価２７の樹脂溶液(ａ−5)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００４８】
製造例６Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリテトラメチレングリコール１６３．８部、ジメチロールブタン酸２９．８部メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート５６．５部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万３千、酸価は４５であった。次に、温度を維持しながら水７４１部、２８％アンモニア水９部を加えこれを水溶化した。
【００４９】
製造例６Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル１．１部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．６、重量平均分子量１４万、酸価４０の樹脂溶液(ａ−6)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００５０】
製造例７Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリテトラメチレングリコール１９５．３部、ジメチロールブタン酸１９．８部メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しヘキサメチレンジイソシアネート３５部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万、酸価は３０であった。次に、温度を維持しながら水７４４．３部、２８％アンモニア水５．８部を加えこれを水溶化した。
【００５１】
製造例７Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−7)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００５２】
製造例８Ａ（プレポリマーの製造）
製造例１Ａと同様な装置に、分子量２０００のポリテトラメチレングリコール１８５部、ジメチロールブタン酸２０部、メチルエチルケトン１００部を加え高真空下１００℃でメチルエチルケトン５０部を留去し、水分を除去した。乾燥窒素雰囲気中で５０℃に冷却しイソホロンジイソシアネート４５部を加えた。発熱反応を利用し徐々に昇温し８０℃、５時間保持した。得られた樹脂の重量平均分子量は４万５千、酸価は３０であった。次に、温度を維持しながら水７０９．８部、ジエチルアミノエタノール４０．３部を加えこれを水溶化した。
【００５３】
製造例８Ｂ（エポキシ化合物との反応）
製造例１Ａと同様な装置に、Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル０．８部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．８、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−8)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００５４】
製造例９（エポキシ化合物との反応）
製造例１Ａと同様な装置に、製造例２Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量２６８のエチレンジグリシジルエーテル１．４部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．４、重量平均分子量１２万、酸価２７の樹脂溶液(ａ−9)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００５５】
製造例１０（エポキシ化合物との反応）
製造例１Ａと同様な装置に、製造例２Ａで得られたウレタン樹脂水溶液４２０部（樹脂分１００部）、エポキシ当量１４３のグリコールポリグリシジルエーテル１．５部を加え昇温し８０℃、１０時間の反応を行った。高真空下１００℃でメチルエチルケトン２０部を留去した。固形分２５％、ｐＨ７．６、重量平均分子量３２万、酸価２４の樹脂溶液(ａ−10)を得た。粗大粒子が無く４０℃２週間でも状態は安定していた。
【００５６】
実施例１（水性印刷インキの製造）
製造例１で得た樹脂溶液（ａ−１）２０．０部 、酸化チタン４０．０、 消泡剤０．１部、 水１９．９部の混合物をペイントコンデイショナーで顔料分散しインキベ−スを得た。次に、製造例１で得た樹脂溶液、水、イソプロピルアルコールを加え印刷インキを作成した。得られた印刷インキにカルボジイミド硬化剤を加え、水／イソプロピルアルコール＝１／１（重量比）の混合溶剤を用いて希釈し、印刷粘度に調整、グラビア印刷機にてポリエチレンテレフタレートフイルム（以下ＰＥＴ）、ナイロンフィルム（以下ＮＹ）に印刷して、塗膜外観、密着性、さらにＮＹについては耐ボイル適性を評価した。
塗膜外観：印刷物の光沢を目視により判定した。
◎非常に光沢がある
○光沢がやや劣る
△光沢がない
×全く光沢がない
密着性評価：印刷物のセロファンテープ剥離試験を行い、印刷皮膜の外観よりその密着性を目視判定した。
◎印刷皮膜が全く剥がれない。
○ 印刷皮膜の２０％以下が剥がれる。
△印刷皮膜の２０％〜５０％が剥がれる。
× 印刷皮膜の５０％以上が剥がれる。
耐ボイル性：ＮＹフイルム上に印刷した印刷インキ面にイソシアネート系接着剤を塗布した後に、押し出しラミネート機によって前記接着剤層上に溶融ポリエチレンを積層し、ラミネート加工物を得た。このラミネート加工物を製袋し、密封後９０℃の熱水中で３０分間加熱し、ラミ状態を外部から目視観察した。
◎全くラミ浮きがない。
○ピンホール状にラミ浮きがでる。
△すじ状にデラミネーションが生じる。
× 全面にデラミネーションが生じる。
結果を表１に示す。
【表１】
実施例２〜１０
製造例２〜１０で得た樹脂溶液(a-2）〜（a-10）を実施例１と同様にそれぞれインキ化、印刷評価を行った。結果を表１に示す。
【００５８】
比較例１〜８
製造例１Ａ〜８Ａで得た（エポキシによる鎖延長を行なっていない）樹脂溶液を実施例１と同様にそれぞれインキ化、印刷評価を行った。結果を表１に示す。
【００５９】
【発明の効果】
実施例、比較例より明らかなように本発明の水性ポリウレタン樹脂は、凝集物もなく、さらに本発明の水性樹脂液を含有する水性印刷インキは、接着性、耐ボイル性に優れ、水性印刷用インキに好適である。[0001]
[Industrial application fields]
The present invention relates to an aqueous polyurethane resin obtained by chain-extending a polyurethane resin with an epoxy compound in an aqueous medium, and an aqueous ink using the aqueous polyurethane resin. The aqueous polyurethane resin obtained by chain extension with the epoxy compound of the present invention is excellent in wettability to plastic films and plastic sheets, adhesiveness, and laminating performance, and is useful in the field of inks, paints and adhesives, especially aqueous printing inks. It is.
[0002]
[Prior art]
Conventionally, polyurethane is a resin that fills the boundary between rubber and plastics by taking advantage of its excellent mechanical properties, wear resistance, chemical resistance, adhesiveness, etc., and it has a wide range of materials such as paints, adhesives, and artificial leather. It has permeated application fields. Under such circumstances, water-based polyurethane has been rapidly developed in order to meet social needs such as environmental protection, resource saving and safety. High-performance water-based polyurethanes have emerged as a result of advances in emulsifying and dispersing technology for urethane resins in water, self-emulsifying and dispersing technology by ionomerization, and high molecular weight technology in water. It has become a comparable level and has been put to practical use in various application fields.
[0003]
However, as a problem of aqueous polyurethane, the emulsifier and ionic group necessary for making it aqueous often impair the inherent properties of the polyurethane resin, such as solvent resistance and heat resistance.
[0004]
Generally, a forced emulsification method, a ketone method, a prepolymer underwater stirring method, a melt dispersion method, a ketimine method, and a self-emulsification method are known for the aqueous polyurethane resin from its production method. Urethane resins used in water-based inks generally have a ketone method, that is, an isocyanate group-containing prepolymer with an organic solvent such as a ketone solvent because of pigment dispersibility, printability, film adhesion, water resistance, etc. After synthesis and neutralization, an aqueous urethane resin such as an emulsion, a colloidal dispersion, and a water-soluble type has been used through a solvent removal process.
[0005]
The polyurethane resin produced by the ketone method requires a solvent removal step in order to obtain an aqueous polyurethane resin. In order to reduce the time and cost required for this solvent removal step, reuse of organic solvents, incineration disposal, etc., for example, JP-A-59-138211 discloses a method of synthesizing and combining polyurethanes in an acrylic monomer. ing. This method generally requires an unsaturated monomer having no active hydrogen, and the reaction between an isocyanate and an unsaturated monomer occurs when a normal unsaturated monomer having active hydrogen is used. There was a drawback that it was difficult to increase the molecular weight of the urethane resin. In addition, this method has drawbacks such as a significant increase in viscosity in the chain extension reaction, and thus the concentration of the urethane resin is lowered or a special stirring device is required.
[0006]
To solve this problem, for example, in JP-A-6-306135, a urethane prepolymer having a terminal isocyanate group is emulsified and dispersed in water and then chain-extended with a polyamine, and an epoxy resin is used as a crosslinking agent. Is disclosed. However, in this method, sufficient adhesion, water resistance and laminate properties cannot be obtained due to the emulsifier used. JP-A-5-295076 discloses a method of emulsifying an isocyanate-terminated prepolymer in water and extending the chain with an amine-terminated epoxy resin. In this method, the adverse effect of the emulsifier is unavoidable.
[0007]
Japanese Patent Application Laid-Open No. 2000-109681 discloses the use of a compound having an epoxy group and a polyvinyl alcohol having an amino group in order to improve performance degradation due to an emulsifier used in the production of an aqueous polyurethane resin. This method provides a certain degree of solvent resistance, but the adhesion is insufficient.
[0008]
Japanese Patent Application Laid-Open No. 11-279236 discloses a method of synthesizing a polyurethane resin in an acrylic monomer having a hydroxyl group as an organic solvent and polymerizing another acrylic monomer after being dispersed in water. This method is effective in omitting the desolvation step, but since the acrylic resin is not combined with the polyurethane resin, the adhesion to the film and the laminate strength are insufficient.
A water-based polyurethane resin using an epoxy resin is also being studied, focusing on the adhesiveness of the epoxy resin, the adhesiveness of the polyurethane resin, and the mechanical properties.
[0009]
[Patent Document 1]
JP 59-138211
[Patent Document 2]
JP-A-6-306135
[Patent Document 3]
JP-A-5-295076
[Patent Document 4]
JP 2000-109681 A
[Patent Document 5]
JP-A-11-279236
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide an aqueous polyurethane resin that does not contain an emulsifier during water phase transition in the production of an aqueous polyurethane resin and is excellent in wettability to a plastic film, adhesiveness, and laminate suitability.
[0011]
[Means for Solving the Problems]
In the present invention, the polyurethane resin is chain-extended with an epoxy compound in an aqueous medium, thereby reducing the deorganic solvent process, excellent pigment dispersibility, and appearance quality (printing effect) of printed matter, and a base material The present inventors have found that an aqueous polyurethane resin having good properties such as adhesion to the resin can be obtained, and that the aqueous polyurethane resin is extremely useful for printing inks, and has led to the present invention.
[0012]
That is, the present invention adds an epoxy compound after obtaining an aqueous dispersion / water-soluble polyurethane resin. And carboxyl groups in the polyurethane resin In the method for producing an aqueous polyurethane resin to be reacted, the epoxy compound has at least two oxirane rings in the molecule, and the epoxy compound is in the range of 0.3 to 20 parts by weight per 100 parts by weight of the polyurethane resin (solid content). A method for producing an aqueous polyurethane resin having a weight average molecular weight of 20,000 to 1500,000 and an acid value of 0.5 to 70. A printing ink comprising an aqueous polyurethane resin obtained by About.
[0013]
Hereafter, the manufacturing method of the aqueous polyurethane resin liquid of this invention is demonstrated.
The polyurethane prepolymer used in the present invention is substantially an isocyanate in a molecule obtained by reacting a high-molecular polyol, an organic diisocyanate and, if necessary, a chain extender in the presence or absence of a solvent. A polyurethane having one or more groups.
[0014]
(Urethane production method)
The production of the polyurethane prepolymer can be carried out by a conventionally known method, and can be carried out at a temperature of 30 to 150 ° C. in the presence or absence of an organic solvent. Examples of organic solvents that can be used include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as dimethylformamide and N-methylpyrrolidone; Aromatic hydrocarbons such as xylene, and the like, and considering the ease of solvent removal after emulsion production, a solvent having a boiling point of less than 100 ° C., such as acetone, methyl ethyl ketone, and ethyl acetate, is more preferable. Further, after the prepolymer is produced, the above organic solvent may be added or added for the purpose of reducing the viscosity or the like.
[0015]
Examples of the polymer polyol that can be used for the production of the polyurethane prepolymer include polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, and polyether polyol. The polyurethane prepolymer is one or more of these polymer polyols. Can be used.
[0016]
(Diol)
Diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, and 3-methyl. Low molecular weight diols such as 1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butylenediol, dipropylene glycol and the like can be used. Also, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butylenediol, dipropylene glycol, etc. Saturated or unsaturated low molecular weight diols or alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, adipic acid, phthalic acid, Isophthalic acid, te Dehydration condensation or polymerization of dicarboxylic acids such as phthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or their anhydrides and dimer acids. Polyester polyols obtained by ring-opening polymerization of a cyclic ester compound; polyester polyols such as polycaprolactone diol; poly-carbonate polyols obtained by reacting a low-molecular diol with carbonate; polybutadiene glycols; bisphenol Examples thereof include polymer polyols usually used in the production of polyurethane resins, such as glycols obtained by adding ethylene oxide or propylene oxide to A, bisphenol F, and hydrogenated bisphenol A.
[0017]
(Isocyanate type)
As the organic diisocyanate, various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Examples include dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, dimerisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group, and the like. be able to.
[0018]
(Acid group type)
Examples of the component that gives an acid group include dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid; glutamine, asparagine, lysine, diaminopropionic acid, Diamine-type amino acids such as ornithine, diaminobenzoic acid, diaminobenzenesulfonic acid; (A-3) glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamine Examples thereof include monoamine type amino acids such as acids. Preferred are 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid.
[0019]
(Urea group chain extension)
Prior to the reaction with the epoxy compound, the polyurethane resin skeleton used in the present invention can be chain-extended by the urea reaction used in ordinary polyurethane resins. The introduction of the urea group makes the chain extension by the epoxy compound effective when the isocyanate group in the isocyanate group-terminated polyurethane resin is 0.1% by weight or more. As the urea group chain extender component, any of chain extenders conventionally used in the production of ordinary polyurethane resins can be used, but it has two or more active hydrogen atoms that can react with isocyanate groups in the molecule. It is preferable to use a low molecular diamine compound having a molecular weight of 300 or less. For example, diamines such as dihydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide; Two or more kinds can be used.
[0020]
(Polyurethane resin polymerization solvent)
Examples of the inert and hydrophilic organic solvent for the isocyanate used in the present invention include ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, dimethylformamide, Amides such as N-methylpyrrolidone and the like can be mentioned, but since polyurethane is usually removed by distillation under reduced pressure, and in order to increase the drying speed even when used without solvent removal, it is preferably lower than water. The use of a boiling solvent is desirable.
[0021]
(Molecular weight of polyurethane resin)
The number average molecular weight of the polymer polyol component needs to be 500 to 10,000. When a polyurethane prepolymer produced using a polymer polyol having a number average molecular weight outside the range of 500 to 10,000 is used, the resulting polyurethane composition has reduced cold resistance, heat resistance, solvent resistance, and the like. Cheap.
[0022]
(Urethane catalyst)
In the production of the polyurethane prepolymer, a reaction catalyst can be added as necessary. Examples of such a catalyst include tin octylate, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, Organotin compounds such as monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate, dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate; triethylamine And tertiary amines such as N, N-diethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, and triethylenediamine.
[0023]
(Method of adding water)
As a method of dispersing the polyurethane resin in water, water may be added dropwise while stirring the prepolymer solution for phase inversion emulsification, or the prepolymer solution may be added dropwise to well-stirred water. Good. Alternatively, a method of dispersing in water while applying a mechanical tension by a homogenizer, a colloid mill or the like is a preferable method. In addition, a method of using ultrasonic waves for water dispersion is also preferable.
[0024]
(Type of neutralizer)
The basic substance for neutralizing the acid group of the polyurethane resin used in the present invention is ammonia; monoethylamine, diethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, monoethanolamine, dimethyl. Organic amines such as ethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-methyl-1-propanol; inorganic alkalis such as sodium hydroxide and potassium hydroxide, and the like. Alternatively, two or more types may be used in combination, but in order to improve the water resistance of the dried film, a water-soluble and highly volatile substance that is easily dissociated by heat is preferable. Particularly, ammonia, trimethylamine, Triethyl Min is preferable.
[0025]
(Method of adding neutralizing agent)
The isocyanate-terminated polyurethane resin is dispersed in water together with ammonia or volatile amine for neutralizing a part or all of the acid component present in the resin. As a method, the water containing alkali is gradually stirred. Alternatively, the resin solution may be added and dispersed and dissolved, or conversely, water containing the resin solution alkali may be gradually added and dispersed and dissolved. The neutralizing agent can be blended simultaneously with the addition of water to the polyurethane resin or after the addition of water, but preferably after the addition of water. Furthermore, when adding water, a small amount of a co-solvent such as methanol, ethanol, propyl alcohol or the like can be used simultaneously with water.
[0026]
(Removal of organic solvent)
The production of the polyurethane resin of the present invention is carried out in the presence or absence of a solvent, but the organic solvent is subjected to a method using a membrane after phase inversion to an aqueous medium or after chain extension reaction with an epoxy compound, or at normal pressure or reduced pressure. Can be removed by distillation.
[0027]
An epoxy compound having at least two or more oxirane rings in the molecule is added to the polyurethane resin thus obtained, and the oxirane ring is opened with one or more of carboxyl group, hydroxyl group and acid anhydride in the polyurethane resin. It is chain extended by ring polymerization.
[0028]
Addition amount
The epoxy group contained in the epoxy compound is added and reacted in the range of 0.3 to 20 parts by weight (solid content) per 100 parts by weight (solid content) of the polyurethane resin. If it is less than 0.5 parts by weight, the adhesion, water resistance and oil resistance are insufficient. If it exceeds 20 parts by weight, not only will the cost be increased, but also viscosity increase and low solidification will occur.
[0029]
(Epoxy reaction conditions)
The temperature at which the epoxy compound is added to the polyurethane resin is preferably 50 to 90 ° C. in order to avoid side reactions of the epoxy compound.
[0030]
(Epoxy compound)
The epoxy compound used in the present invention is a resin made of polyglycidyl ether of monoalkyl alcohol or polyvalent alkyl alcohol. The epoxy equivalent of these epoxy compounds is preferably 100 to 2000, particularly preferably 100 to 1000.
[0031]
The epoxy compound is a resin having one or more oxysilane rings in the molecule. Compounds having two or more oxysilane rings in the molecule include bisphenol A diglycidyl ether, bisphenol A diβ methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol. A diglycidyl ether, chlorinated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, novolac glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol Diglycidyl ether, glycidyl ether such as epoxy urethane resin Glycidyl ether ester type such as P-oxybenzoic acid glycidyl ether ester; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid diglycidyl ester, dimer acid diglycidyl Glycidyl ester types such as esters; Glycidyl amine types such as glycidyl aniline, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, and triglycidyl aminophenol; Linear aliphatic epoxy compounds such as epoxidized polybutadiene and epoxidized soybean oil; Epoxy-6 methylcyclohexylmethyl-3,4 epoxy-6 methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy Hexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, limonene dioxide and other alicyclic epoxies Compound etc. are mentioned.
[0032]
Among these, water-soluble epoxy compounds are preferable, and examples thereof include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2 -Hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, ethylene / propylene glycol diglycidyl ether and the like.
[0033]
Reaction of urethane with other resins
Also, an aqueous / water-dispersible resin other than polyurethane having either a carboxyl group, a hydroxyl group, an acid anhydride, or two or more reactive groups,
It can be made to react with a polyurethane resin through an epoxy compound.
Examples of the aqueous or water-dispersed resin having a reactive group include various resins such as acrylic resin, polyolefin resin, polyvinyl alcohol, polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, and polyether polyol.
[0034]
Molecular weight
When using the said water-based polyurethane resin as a printing ink use, Preferably a weight average molecular weight is the range of 20000-1500000, More preferably, it is the range of 30000-500000. When it is less than 20000, blocking resistance, water resistance and laminate suitability are lowered. If it exceeds 1500,000, the pigment dispersibility and re-dissolvability will decrease.
[0035]
Acid value
Similarly, the acid value is preferably in the range of 0.5 to 70, more preferably 20 to 50. When it is less than 0.5, the stability of the ink is lowered, and when it is more than 70, the water resistance and the suitability for lamination are lowered.
[0036]
In the water-based printing ink of the present invention, in addition to the above-mentioned water-based polyurethane resin, water-based resins such as shellac, rosin-modified maleic acid resin, water-based acrylic resin, water-based polyester resin, and existing water-based polyurethane resin are used according to the present invention. It can be blended as long as the purpose is not hindered. Furthermore, in order to give the necessary properties as water-based printing ink, coloring agents such as pigments, extender pigments, waxes, antifoaming agents, thickeners, curing agents, water and water-miscible organic solvents are used as necessary. A water-based printing ink is produced by appropriately adding, dispersing using a kneader such as an attritor or sand mill, and adjusting the viscosity to a predetermined viscosity. The aqueous printing ink thus obtained is diluted with water or a water-miscible organic solvent such as ethyl alcohol, isopropyl alcohol, normal propyl alcohol or the like mixed with a solvent until a suitable viscosity is obtained during printing, Printed on plastic film etc. by gravure printing or flexographic printing.
[0037]
The aqueous polyurethane dispersion obtained by the method of the present invention has excellent adhesion to films and metal surfaces, and has excellent water resistance and mechanical properties. In the printing ink field, excellent printability and lamination suitability can be obtained. Moreover, it can be painted using spray coating, roll coating or the like to obtain a good coating film. In particular, it is excellent in paintability for inorganic materials such as metals, and can be used for many applications that could not be applied with conventional polyurethane aqueous resin liquids. A wide range of applications, including automotive and household paint vehicles, glass plastics, fabrics, paper, leather, wood, metal coatings, thin film coatings for fibers and fabrics, surface coatings for fur, and various adhesives Can be used.
【Example】
Next, the present invention will be further described with reference to examples. Unless otherwise indicated, parts and% in this example are based on weight.
[0038]
Production Example 1A (Prepolymer production)
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 184.8 parts of polytetramethylene glycol having a molecular weight of 2000 and 20 parts of dimethylolbutanoic acid, and heat at 100 ° C. for 20 minutes under high vacuum. Was removed. Cool to 50 ° C. in a dry nitrogen atmosphere and add 45.3 parts of isophorone diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The obtained resin had a weight average molecular weight of 45,000 and an acid value of 30. Next, while maintaining the temperature, 644.3 parts of water, 5.8 parts of 28% ammonia water, and 100 parts of isopropyl alcohol were added to make it water-soluble.
[0039]
Production Example 1B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 400 parts of the urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added and the temperature was raised. Went. A resin solution (a-1) having a solid content of 25%, a pH of 7.6, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0040]
Production Example 2A (Prepolymer production)
Add 332.6 parts of polytetramethylene glycol having a molecular weight of 2000, 36 parts of dimethylolbutanoic acid and 180 parts of methyl ethyl ketone to the same apparatus as in Production Example 1A, and distill off 90 parts of methyl ethyl ketone at 100 ° C. under high vacuum to remove moisture. did. The mixture was cooled to 50 ° C. in a dry nitrogen atmosphere, and 81.5 parts of isophorone diisocyanate was added. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 40,000, and the acid value was 30. Next, while maintaining the temperature, 1339.7 parts of water and 10.4 parts of 28% aqueous ammonia were added to make it water-soluble.
[0041]
Production Example 2B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-2) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0042]
Production Example 3A (Prepolymer Production)
In the same device as in Production Example 1A,
183 parts of copolymerized polytetramethylene ether glycol (Asahi Kasei Corporation PTXG1800) having a molecular weight of 1800 and 20 parts of dimethylolbutanoic acid 100 parts of methyl ethyl ketone were added, and 50 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum to remove water. Cool to 50 ° C. in a dry nitrogen atmosphere and add 47 parts of isophorone diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 40,000, and the acid value was 30. Next, while maintaining the temperature, 744.3 parts of water and 5.8 parts of 28% aqueous ammonia were added to make it water-soluble.
[0043]
Production Example 3B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-3) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 1,200,000 and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0044]
Production Example 4A (Prepolymer production)
184.8 parts of polypropylene adipate having a molecular weight of 2000 and 20 parts of dimethylolbutanoic acid 100 parts of methyl ethyl ketone were added to the same apparatus as in Production Example 1A, and 50 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum to remove moisture. Cool to 50 ° C. in a dry nitrogen atmosphere and add 45.3 parts of isophorone diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 40,000, and the acid value was 30. Next, while maintaining the temperature, 744.3 parts of water and 5.8 parts of 28% aqueous ammonia were added to make it water-soluble.
[0045]
Production Example 4B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-4) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0046]
Production Example 5A (Prepolymer production)
In the same apparatus as in Production Example 1A, 180 parts of polytetramethylene glycol having a molecular weight of 2000, 3.5 parts of polyethylene glycol having a molecular weight of 400, 20 parts of dimethylolbutanoic acid and 100 parts of methyl ethyl ketone were added, and 50 parts of methyl ethyl ketone was added at 100 ° C. under high vacuum. Distilled off to remove moisture. The mixture was cooled to 50 ° C. in a dry nitrogen atmosphere, and 46.5 parts of isophorone diisocyanate was added. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The obtained resin had a weight average molecular weight of 34,000 and an acid value of 30. Next, while maintaining the temperature, 744.3 parts of water and 5.8 parts of 28% aqueous ammonia were added to make it water-soluble.
[0047]
Production Example 5B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-5) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 100,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0048]
Production Example 6A (Prepolymer production)
In a device similar to Production Example 1A, 163.8 parts of polytetramethylene glycol having a molecular weight of 2000, 29.8 parts of dimethylolbutanoic acid and 100 parts of methyl ethyl ketone were added, and 50 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum to remove moisture. Removed. Cool to 50 ° C. in a dry nitrogen atmosphere and add 56.5 parts of isophorone diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The obtained resin had a weight average molecular weight of 43,000 and an acid value of 45. Next, while maintaining the temperature, 741 parts of water and 9 parts of 28% aqueous ammonia were added to make it water-soluble.
[0049]
Production Example 6B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of the urethane resin aqueous solution obtained in A (100 parts of resin) and 1.1 parts of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-6) having a solid content of 25%, a pH of 7.6, a weight average molecular weight of 140,000, and an acid value of 40 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0050]
Production Example 7A (Prepolymer Production)
In the same apparatus as in Production Example 1A, 195.3 parts of polytetramethylene glycol having a molecular weight of 2000, 19.8 parts of dimethylolbutanoic acid and 100 parts of methyl ethyl ketone were added, 50 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum, and water was removed. Removed. Cool to 50 ° C. in a dry nitrogen atmosphere and add 35 parts of hexamethylene diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 40,000, and the acid value was 30. Next, while maintaining the temperature, 744.3 parts of water and 5.8 parts of 28% aqueous ammonia were added to make it water-soluble.
[0051]
Production Example 7B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-7) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0052]
Production Example 8A (Prepolymer production)
In the same apparatus as in Production Example 1A, 185 parts of polytetramethylene glycol having a molecular weight of 2000, 20 parts of dimethylolbutanoic acid, and 100 parts of methyl ethyl ketone were added, and 50 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum to remove moisture. Cool to 50 ° C. in a dry nitrogen atmosphere and add 45 parts of isophorone diisocyanate. Using an exothermic reaction, the temperature was gradually raised and maintained at 80 ° C. for 5 hours. The obtained resin had a weight average molecular weight of 45,000 and an acid value of 30. Next, while maintaining the temperature, 709.8 parts of water and 40.3 parts of diethylaminoethanol were added to make it water-soluble.
[0053]
Production Example 8B (reaction with epoxy compound)
In the same apparatus as in Production Example 1A, 420 parts of urethane resin aqueous solution obtained in A (100 parts of resin) and 0.8 part of glycol polyglycidyl ether having an epoxy equivalent of 143 were added, and the temperature was raised and the reaction was carried out at 80 ° C. for 10 hours. Went. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-8) having a solid content of 25%, a pH of 7.8, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0054]
Production Example 9 (Reaction with Epoxy Compound)
In the same apparatus as in Production Example 1A, 420 parts of the urethane resin aqueous solution obtained in Production Example 2A (resin content: 100 parts) and 1.4 parts of ethylenediglycidyl ether having an epoxy equivalent of 268 were added and heated to 80 ° C. for 10 hours. The reaction was performed. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-9) having a solid content of 25%, a pH of 7.4, a weight average molecular weight of 120,000, and an acid value of 27 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0055]
Production Example 10 (Reaction with Epoxy Compound)
To the same apparatus as in Production Example 1A, 420 parts of the urethane resin aqueous solution obtained in Production Example 2A (resin content: 100 parts) and 1.5 parts of glycol polyglycidyl ether having an epoxy equivalent of 143 were added and heated to 80 ° C. for 10 hours. The reaction was performed. 20 parts of methyl ethyl ketone was distilled off at 100 ° C. under high vacuum. A resin solution (a-10) having a solid content of 25%, a pH of 7.6, a weight average molecular weight of 320,000, and an acid value of 24 was obtained. There were no coarse particles and the state was stable even at 40 ° C. for 2 weeks.
[0056]
Example 1 (Production of water-based printing ink)
A mixture of 20.0 parts of the resin solution (a-1) obtained in Production Example 1, 40.0 titanium oxide, 0.1 part of an antifoaming agent, and 19.9 parts of water was dispersed in a pigment with a paint conditioner to obtain an ink base. I got. Next, the resin solution obtained in Production Example 1, water, and isopropyl alcohol were added to prepare a printing ink. Carbodiimide curing agent is added to the obtained printing ink, diluted with a mixed solvent of water / isopropyl alcohol = 1/1 (weight ratio), adjusted to the printing viscosity, polyethylene terephthalate film (hereinafter referred to as PET) with a gravure printing machine. The film was printed on a nylon film (hereinafter referred to as “NY”), and the appearance and adhesion of the coating film were evaluated.
Appearance of coating film: The gloss of the printed matter was visually determined.
◎ very shiny
○ Slightly inferior in gloss
△ No gloss
× No gloss
Adhesion evaluation: A cellophane tape peeling test was performed on the printed matter, and the adhesion was visually determined from the appearance of the printed film.
◎ The printed film does not peel off at all.
○ 20% or less of the printed film is peeled off.
Δ 20% to 50% of the printed film is peeled off.
X 50% or more of the printed film is peeled off.
Boil resistance: An isocyanate adhesive was applied to the printing ink surface printed on the NY film, and then molten polyethylene was laminated on the adhesive layer by an extrusion laminating machine to obtain a laminated product. The laminated product was made into a bag, and after sealing, heated in 90 ° C. hot water for 30 minutes, and the laminated state was visually observed from the outside.
◎ There is no Lami float.
○ Lami floats like a pinhole.
Δ Delamination occurs in a streak shape.
× Delamination occurs on the entire surface.
The results are shown in Table 1.
[Table 1]
Examples 2-10
The resin solutions (a-2) to (a-10) obtained in Production Examples 2 to 10 were inked and evaluated for printing in the same manner as in Example 1. The results are shown in Table 1.
[0058]
Comparative Examples 1-8
The resin solutions obtained in Production Examples 1A to 8A (not subjected to chain extension by epoxy) were inked and evaluated for printing in the same manner as in Example 1. The results are shown in Table 1.
[0059]
【The invention's effect】
As is clear from the examples and comparative examples, the aqueous polyurethane resin of the present invention has no aggregates, and the aqueous printing ink containing the aqueous resin liquid of the present invention is excellent in adhesion and boil resistance, and is suitable for aqueous printing. Suitable for ink.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003093228A JP4345335B2 (en) | 2003-03-31 | 2003-03-31 | Water-based polyurethane resin and printing ink using the resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003093228A JP4345335B2 (en) | 2003-03-31 | 2003-03-31 | Water-based polyurethane resin and printing ink using the resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004300223A JP2004300223A (en) | 2004-10-28 |
| JP4345335B2 true JP4345335B2 (en) | 2009-10-14 |
Family
ID=33406078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003093228A Expired - Fee Related JP4345335B2 (en) | 2003-03-31 | 2003-03-31 | Water-based polyurethane resin and printing ink using the resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4345335B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100874302B1 (en) * | 2005-02-18 | 2008-12-18 | 도요 잉키 세이조 가부시끼가이샤 | Electromagnetic shielding adhesive film, manufacturing method thereof and electromagnetic shielding method of adherend |
| JP5549387B2 (en) * | 2010-06-04 | 2014-07-16 | 東洋インキＳｃホールディングス株式会社 | Non-yellowing water-soluble printing ink composition |
| WO2012035827A1 (en) * | 2010-09-17 | 2012-03-22 | Dic株式会社 | Binder for inkjet printing ink, inkjet printing ink containing same, and printed matter |
| JP5831022B2 (en) * | 2011-08-04 | 2015-12-09 | Dic株式会社 | Method for producing a binder for ink jet printing ink |
| JP6330603B2 (en) * | 2014-09-19 | 2018-05-30 | 東洋インキＳｃホールディングス株式会社 | Water-based ink resin composition and water-based ink composition |
| JP7187438B2 (en) * | 2017-03-22 | 2022-12-12 | 株式会社Adeka | Aqueous polyurethane resin composition |
| JP2020193321A (en) | 2019-05-27 | 2020-12-03 | 花王株式会社 | Water-based ink for printing with printing plate |
| EP4079822A4 (en) * | 2019-12-20 | 2023-12-13 | DIC Corporation | Urethane resin aqueous dispersion, synthetic leather, and method for producing synthetic leather |
| CN111732850B (en) * | 2020-07-15 | 2022-11-08 | 沾化神茂皮革助剂有限公司 | Formula of waterborne polyurethane ink binder for food flexible packaging and preparation method thereof |
| CN113528246B (en) * | 2021-05-21 | 2024-04-12 | 东莞市浩彩油墨科技有限公司 | Preparation method of multifunctional water-based vegetable oil binder and water-based ink |
-
2003
- 2003-03-31 JP JP2003093228A patent/JP4345335B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004300223A (en) | 2004-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3493796B2 (en) | Waterborne polyurethane resin paint | |
| JP3001358B2 (en) | Aqueous printing ink composition for plastic film, adhesive for aqueous lamination, and method for producing a laminated product using the same | |
| JP4345335B2 (en) | Water-based polyurethane resin and printing ink using the resin | |
| GB2382545A (en) | Coated film and method of laminating the same | |
| JP2019112583A (en) | Ink set and decorative material | |
| JP5035742B2 (en) | Aqueous polyurethane emulsion composition | |
| JPH11323300A (en) | Polyurethane emulsion for aqueous adhesive and aqueous adhesive produced by using the emulsion | |
| JPH11228655A (en) | Polyurethane-based emulsion for water-based printing ink and water-based printing ink using the same | |
| JPH11293191A (en) | Polyurethane-based emulsion for aqueous printing ink, and aqueous printing ink using the same | |
| JP3767034B2 (en) | Self-crosslinking water-based polyurethane resin, process for producing the same, and water-based printing ink using the same as a binder | |
| JPH0827243A (en) | Aqueous polyurethane resin and its production | |
| JP3255953B2 (en) | Aqueous printing ink composition for lamination | |
| JP3047586B2 (en) | Polyurethane having rosin skeleton | |
| JPH10152639A (en) | Water-base printing ink | |
| JP2004115670A (en) | Polyurethane resin and printing ink using the same | |
| JP2005048046A (en) | Adhesive for dry laminate | |
| JPH101636A (en) | Water-base printing ink and its production | |
| JPH07157526A (en) | Production of self-emulsifiable urethane emulsion | |
| JPH0680754A (en) | Water-base polyurethane having rosin backbone | |
| JPH05302050A (en) | Printing ink | |
| JP4573155B2 (en) | Water-based polyurethane resin, water-based polyurethane resin aqueous dispersion, printing ink binder and printing ink composition | |
| JPH0827242A (en) | Aqueous polyurethane resin and its production | |
| JP3214288B2 (en) | Printing ink composition and printed matter | |
| JPH11279471A (en) | Water-based printing ink composition | |
| JPH0649404A (en) | Printing ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050915 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071218 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071225 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20080221 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20080226 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080321 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080930 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081022 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090331 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090406 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20090518 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090623 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090706 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4345335 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120724 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120724 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120724 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130724 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130724 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140724 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |