JP2021088690A - Gravure print ink composition for surface printing and printed matter - Google Patents
Gravure print ink composition for surface printing and printed matter Download PDFInfo
- Publication number
- JP2021088690A JP2021088690A JP2019226103A JP2019226103A JP2021088690A JP 2021088690 A JP2021088690 A JP 2021088690A JP 2019226103 A JP2019226103 A JP 2019226103A JP 2019226103 A JP2019226103 A JP 2019226103A JP 2021088690 A JP2021088690 A JP 2021088690A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- ink composition
- parts
- gravure printing
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000003854 Surface Print Methods 0.000 title claims abstract description 12
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 22
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 12
- 239000001913 cellulose Substances 0.000 claims abstract description 12
- 238000007639 printing Methods 0.000 claims description 53
- 238000007646 gravure printing Methods 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 17
- 229920005906 polyester polyol Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000903 blocking effect Effects 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- QGEOKXWFGANCJL-UHFFFAOYSA-N ethenyl acetate;hydrochloride Chemical compound Cl.CC(=O)OC=C QGEOKXWFGANCJL-UHFFFAOYSA-N 0.000 abstract 1
- -1 aliphatic diols Chemical class 0.000 description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 14
- 229940090181 propyl acetate Drugs 0.000 description 14
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 14
- 125000003277 amino group Chemical group 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 11
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical group NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 11
- 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 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 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 10
- 239000004970 Chain extender Substances 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000020 Nitrocellulose Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920002301 cellulose acetate Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 1
- IBUPNDMHIOTKBL-UHFFFAOYSA-N 1,5-diaminopentan-2-ol Chemical group NCCCC(O)CN IBUPNDMHIOTKBL-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
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- 240000000972 Agathis dammara Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Chemical group 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PPKVREKQVQREQD-UHFFFAOYSA-N antimony pentasulfide Chemical compound S=[Sb](=S)S[Sb](=S)=S PPKVREKQVQREQD-UHFFFAOYSA-N 0.000 description 1
- 229960001283 antimony pentasulfide Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 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 1
- 235000008429 bread Nutrition 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical class CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、表刷り用グラビア印刷インキ組成物および印刷物に関する。 The present invention relates to a gravure printing ink composition for front printing and a printed matter.
パン、おにぎり、野菜等の商品の包装には、装飾や表面保護のために表刷り用グラビア印刷インキ組成物を樹脂フィルムの表側に印刷する（表刷り印刷方式といわれる）印刷物が利用されている。とくに、上記の包装に使用される基材には、内容物由来の水蒸気で曇らないように、基材の内容物側が防曇性を有する防曇フィルムが使用されている。 For packaging products such as bread, rice balls, and vegetables, printed matter in which a gravure printing ink composition for front printing is printed on the front side of a resin film (called a front printing method) is used for decoration and surface protection. .. In particular, as the base material used for the above packaging, an antifogging film having an antifogging property on the content side of the base material is used so as not to be fogged by water vapor derived from the contents.
このような用途に適した表刷り用グラビア印刷インキ組成物としては、例えば、特許文献１では、顔料、バインダー樹脂、キレート架橋剤、脂肪酸アミドおよび有機溶媒を含有し、前記バインダー樹脂が、特定量のウレア結合を有するポリウレタン樹脂とウレア結合を有さないポリウレタン樹脂を含有するものが知られている。また、特許文献２では、ポリウレタン樹脂、塩化ビニル−酢酸ビニル共重合樹脂、顔料および有機溶剤を含有し、前記ポリウレタン樹脂は、ポリオール由来の構造単位を有し、ポリオール由来の構造単位は、特定量の、数平均分子量が３００以上の高分子ポリオール由来の構造単位と、分子量が１８０以下の脂肪族ジオール由来の構造単位を含有するものが知られている。 As a gravure printing ink composition for front printing suitable for such applications, for example, in Patent Document 1, a pigment, a binder resin, a chelate cross-linking agent, a fatty acid amide and an organic solvent are contained, and the binder resin is contained in a specific amount. It is known that a polyurethane resin having a urea bond and a polyurethane resin having no urea bond are contained. Further, in Patent Document 2, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, a pigment and an organic solvent are contained, the polyurethane resin has a structural unit derived from a polyol, and the structural unit derived from the polyol is a specific amount. There are known structural units derived from high molecular weight polyols having a number average molecular weight of 300 or more and structural units derived from aliphatic diols having a molecular weight of 180 or less.
一方、上記のような用途では、手についたアルコール（例えば、除菌用アルコールなど）などによって、表刷り用グラビア印刷インキ組成物から形成される印刷層が剥がれ落ちる問題があったため、上記の特許文献で開示された表刷り用グラビア印刷インキ組成物には、耐アルコール性について、改善の余地があった。 On the other hand, in the above-mentioned applications, there is a problem that the printing layer formed from the gravure printing ink composition for front printing is peeled off due to alcohol on the hands (for example, alcohol for disinfection). The gravure printing ink composition for front printing disclosed in the literature has room for improvement in alcohol resistance.
また、とくに、基材として防曇フィルムを使用した場合、印刷物を巻きの状態で保管している際に、防曇性を有する面（非印刷面）が、印刷面のインキを剥離してしまい易い（ブロッキング現象が生じやすい）傾向にあったため、防曇フィルムに対する耐ブロッキング性を有する印刷物が求められていた。 In particular, when an anti-fog film is used as the base material, the anti-fog surface (non-printing surface) peels off the ink on the printed surface when the printed matter is stored in a rolled state. Since it tends to be easy (blocking phenomenon is likely to occur), a printed matter having blocking resistance against an antifogging film has been required.
本発明は、上記の実情に鑑みてなされたものであり、耐アルコール性、および防曇フィルムに対する耐ブロッキング性に優れた表刷り用グラビア印刷インキ組成物およびその印刷物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a gravure printing ink composition for surface printing and a printed matter thereof, which are excellent in alcohol resistance and blocking resistance against an antifogging film. ..
すなわち、本発明は、顔料、ポリウレタン樹脂、セルロース誘導体及び／又は塩化ビニル酢酸ビニル共重合体、脂肪酸アミド、ならびに有機溶媒を含有する表刷り用グラビア印刷インキ組成物であって、前記ポリウレタン樹脂は、ポリオール由来の構造単位として、ポリテトラメチレンエーテルグリコール由来の構造単位を有する表刷り用グラビア印刷インキ組成物に関する。 That is, the present invention is a gravure printing ink composition for surface printing containing a pigment, a polyurethane resin, a cellulose derivative and / or a vinyl chloride vinyl acetate copolymer, a fatty acid amide, and an organic solvent. The present invention relates to a gravure printing ink composition for printing, which has a structural unit derived from polytetramethylene ether glycol as a structural unit derived from a polyol.
また、本発明は、基材に、前記表刷り用グラビア印刷インキ組成物から形成される印刷層が設けられている印刷物に関する。 The present invention also relates to a printed matter in which a printing layer formed from the gravure printing ink composition for front printing is provided on a base material.
本発明の表刷り用グラビア印刷インキ組成物における効果の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。ただし、本発明は、この作用メカニズムに限定して解釈されなくてもよい。 The details of the action mechanism of the effect in the gravure printing ink composition for front printing of the present invention are unknown, but it is presumed as follows. However, the present invention does not have to be construed as being limited to this mechanism of action.
本発明の表刷り用グラビア印刷インキ組成物は、顔料、ポリウレタン樹脂、セルロース誘導体及び／又は塩化ビニル酢酸ビニル共重合体、脂肪酸アミド、ならびに有機溶媒を含有し、前記ポリウレタン樹脂は、ポリオール由来の構造単位として、ポリテトラメチレンエーテルグリコール由来の構造単位を有する。従前のポリウレタン樹脂は、ポリオール成分として、ポリエステルポリオールやポリプロピレングリコール等を用いることが一般的であったが、ポリエステルポリオールは耐アルコール性に比較的優れる一方、防曇フィルムに対する耐ブロッキング性が比較的劣る傾向があり、ポリプロピレングリコールはその逆の傾向であることから、耐アルコール性と防曇フィルムに対する耐ブロッキング性が相反関係となるため、従前の表刷り用グラビア印刷インキ組成物では、両者を同時に発現させることは困難であった。一方、本発明のポリウレタン樹脂を構成するポリテトラメチレンエーテルグリコールは、特許文献１や２で具体的に開示されたポリプロピレングリコールよりも、炭素鎖が長く疎水性であり、加えて、ポリウレタン樹脂に導入されるエーテル結合が少なくなるため、耐アルコール性を向上させることができると推定される。また、ポリテトラメチレンエーテルグリコールは、炭素鎖が直鎖であることにより結晶性が高いため、印刷層（塗膜）が強靭となり、防曇フィルムに対する耐ブロッキング性を向上させることができると推定される。よって、本発明の表刷り用グラビア印刷インキ組成物は、耐アルコール性、および防曇フィルムに対する耐ブロッキング性を同時に発現する。 The gravure printing ink composition for surface printing of the present invention contains a pigment, a polyurethane resin, a cellulose derivative and / or a vinyl chloride vinyl acetate copolymer, a fatty acid amide, and an organic solvent, and the polyurethane resin has a structure derived from a polyol. As a unit, it has a structural unit derived from polytetramethylene ether glycol. Conventional polyurethane resins generally use polyester polyol, polypropylene glycol, or the like as a polyol component, but polyester polyol is relatively excellent in alcohol resistance, but relatively inferior in blocking resistance to antifogging film. Since there is a tendency and polypropylene glycol has the opposite tendency, alcohol resistance and blocking resistance against antifogging film have a reciprocal relationship. Therefore, in the conventional gravure printing ink composition for front printing, both are expressed at the same time. It was difficult to get it done. On the other hand, the polytetramethylene ether glycol constituting the polyurethane resin of the present invention has a longer carbon chain and is more hydrophobic than the polypropylene glycol specifically disclosed in Patent Documents 1 and 2, and is additionally introduced into the polyurethane resin. It is presumed that the alcohol resistance can be improved because the amount of ether bonds formed is reduced. Further, it is presumed that polytetramethylene ether glycol has high crystallinity due to its straight carbon chain, so that the printed layer (coating film) becomes tough and the blocking resistance against the antifogging film can be improved. To. Therefore, the gravure printing ink composition for front printing of the present invention simultaneously exhibits alcohol resistance and blocking resistance against an antifogging film.
本発明の表刷り用グラビア印刷インキ組成物は、顔料、ポリウレタン樹脂、セルロース誘導体及び／又は塩化ビニル酢酸ビニル共重合体、脂肪酸アミド、ならびに有機溶媒を含有し、前記ポリウレタン樹脂は、ポリオール由来の構造単位として、ポリテトラメチレンエーテルグリコール由来の構造単位を有する。 The gravure printing ink composition for surface printing of the present invention contains a pigment, a polyurethane resin, a cellulose derivative and / or a vinyl chloride vinyl acetate copolymer, a fatty acid amide, and an organic solvent, and the polyurethane resin has a structure derived from a polyol. As a unit, it has a structural unit derived from polytetramethylene ether glycol.
＜顔料＞
本発明の顔料は、一般に有機溶媒を含有するグラビア印刷インキ組成物で使用される、無機顔料、有機顔料、体質顔料が使用できる。前記無機顔料としては、例えば、酸化チタン、ベンガラ、アンチモンレッド、カドミウムレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛などが挙げられ、また、前記有機顔料としては、例えば、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料などが挙げられ、さらに前記体質顔料としては、例えば、炭酸カルシウム、カオリンクレー、硫酸バリウム、水酸化アルミニウム、タルクなどを挙げられる。前記顔料は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。
<Pigment>
As the pigment of the present invention, inorganic pigments, organic pigments, and extender pigments generally used in gravure printing ink compositions containing an organic solvent can be used. Examples of the inorganic pigment include titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine, carbon black, graphite and the like, and examples of the organic pigment include soluble azo. Examples thereof include pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the extender pigments include, for example, calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, talc and the like. Can be mentioned. At least one of the pigments may be used, and two or more of the pigments may be used in combination.
＜ポリウレタン樹脂＞
本発明のポリウレタン樹脂は、分子中に２個以上のウレタン結合を有する樹脂であり、ポリオール由来の構造単位として、ポリテトラメチレンエーテルグリコール由来の構造単位を有すれば、特に制限なく使用でき、例えば、ポリイソシアネート化合物、ポリテトラメチレンエーテルグリコールを含むポリオール化合物、鎖伸長剤、および反応停止剤を反応して得られる（ポリイソシアネート化合物とポリテトラメチレンエーテルグリコールを含むポリオール化合物を反応させて得られたウレタンプレポリマーに、さらに、鎖伸長剤および反応停止剤を反応させて得られる）ポリウレタン樹脂などが挙げられる。前記ポリウレタン樹脂は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。
<Polyurethane resin>
The polyurethane resin of the present invention is a resin having two or more urethane bonds in its molecule, and can be used without particular limitation as long as it has a structural unit derived from polytetramethylene ether glycol as a structural unit derived from polyol, for example. , Polyisocyanate compound, polyol compound containing polytetramethylene ether glycol, chain extender, and reaction terminator (obtained by reacting a polyisocyanate compound with a polyol compound containing polytetramethylene ether glycol). Examples thereof include polyurethane resin (obtained by reacting a chain extender and a reaction terminator with a urethane prepolymer). At least one type of the polyurethane resin may be used, and two or more types may be used in combination.
前記ポリイソシアネート化合物としては、ジイソシアネート化合物を使用することが好ましく、例えば、ヘキサ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などの脂肪族ジイソシアネート化合物；イソホロンジイソシアネート、水添キシリレンジイソシアネートなどの脂環族ジイソシアネート化合物；キシリレンジイソシアネート、α，α，α’，α’−テトラメチルキシリレンジイソシアネートなどの芳香脂肪族ジイソシアネート化合物；トルイレンジイソシアネート、ジフェニルメタンジイソシアネートなどの芳香族ジイソシアネート化合物などが挙げられる。これらの中でも、反応の制御が簡単で、得られるポリウレタン樹脂の性能のバランスが良好である観点から、脂環族または芳香脂肪族ジイソシアネート化合物が好ましく、特に、イソホロンジイソシアネート、α，α，α’，α’−テトラメチルキシリレンジイソシアネートが好ましい。前記ジイソシアネート化合物は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。 As the polyisocyanate compound, it is preferable to use a diisocyanate compound, for example, an aliphatic diisocyanate compound such as hexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate; or a fat such as isophorone diisocyanate or hydrogenated xylylene diisocyanate. Cyclical diisocyanate compounds; aromatic aliphatic diisocyanate compounds such as xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate; aromatic diisocyanate compounds such as toluylene diisocyanate and diphenylmethane diisocyanate can be mentioned. Among these, alicyclic or aromatic aliphatic diisocyanate compounds are preferable from the viewpoint of easy reaction control and a good balance of performance of the obtained polyurethane resin, and in particular, isophorone diisocyanate, α, α, α', α'-Tetramethylxylylene diisocyanate is preferred. At least one type of the diisocyanate compound may be used, and two or more types may be used in combination.
前記ポリテトラメチレンエーテルグリコールは、一般式（１）：ＨＯ−（ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−Ｏ）ｎ−Ｈで表される化合物である。前記ポリテトラメチレンエーテルグリコールは、ポリウレタンとした時の諸物性付与の観点から、数平均分子量が２５０以上であることが好ましく、５００以上であることがより好ましく、７５０以上であることがさらに好ましく、そして、イソシアネートとの反応性の観点から、数平均分子量が５，０００以下であることが好ましく、４，０００以下であることがより好ましく、３，０００以下であることがさらに好ましい。なお、当該数平均分子量は、以下の式にて算出できる。式：数平均分子量＝１０００×５６．１×水酸基の価数／水酸基価。 The polytetramethylene ether glycol is a compound represented by the general formula (1): HO- (CH 2- CH 2- CH 2- CH 2- O) n-H. The polytetramethylene ether glycol preferably has a number average molecular weight of 250 or more, more preferably 500 or more, still more preferably 750 or more, from the viewpoint of imparting various physical properties when it is made into polyurethane. From the viewpoint of reactivity with isocyanate, the number average molecular weight is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less. The number average molecular weight can be calculated by the following formula. Formula: Number average molecular weight = 1000 x 56.1 x hydroxyl valence / hydroxyl value.
前記ポリオール化合物は、前記ポリテトラメチレンエーテルグリコール以外のポリオール化合物（その他のポリオール化合物）を含んでもよく、例えば、ポリエステルジオール化合物などのポリエステルポリオール化合物、ポリエーテルジオール化合物などのポリエーテルポリオール化合物（ただし、上記の前記ポリテトラメチレンエーテルグリコールを除く）、ポリカーボネートジオール化合物などのポリカーボネートポリオール化合物、ポリブタジエングリコール化合物などの高分子ジオールなどが挙げられる。その他のポリオール化合物は、２種以上を組み合わせて用いることができる。 The polyol compound may contain a polyol compound other than the polytetramethylene ether glycol (other polyol compounds), for example, a polyester polyol compound such as a polyester diol compound, a polyether polyol compound such as a polyether diol compound (however, however). (Excluding the above-mentioned polytetramethylene ether glycol), polycarbonate polyol compounds such as polycarbonate diol compounds, polymer diols such as polybutadiene glycol compounds, and the like can be mentioned. Other polyol compounds can be used in combination of two or more.
前記ポリエステルポリオール化合物としては、例えば、低分子ジオール成分（エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールなどの直鎖状グリコール類；１，２−プロパンジオール、ネオペンチルグリコール、３−メチル−１，５−ペンタンジオール、２，４−ジエチル−１，５−ペンタンジオールなどの分岐グリコール類；ジエチレングリコール、トリエチレングリコールなどのエーテル系ジオール類）と、ジカルボン酸成分（コハク酸、アジピン酸、マレイン酸などの飽和および不飽和脂肪族ジカルボン酸類；フタル酸などの芳香族ジカルボン酸類）を反応させて得られるポリエステルジオール化合物などが挙げられる。 Examples of the polyester polyol compound include linear glycols such as low molecular weight diol components (ethylene glycol, 1,3-propanediol, and 1,4-butanediol; 1,2-propanediol, neopentyl glycol, 3). -Branched glycols such as methyl-1,5-pentanediol and 2,4-diethyl-1,5-pentanediol; ether-based diols such as diethylene glycol and triethylene glycol) and dicarboxylic acid components (succinic acid and adipine). Examples thereof include polyesterdiol compounds obtained by reacting saturated and unsaturated aliphatic dicarboxylic acids such as acid and maleic acid; aromatic dicarboxylic acids such as phthalic acid).
前記ポリエーテルポリオール化合物としては、例えば、環状エステル化合物（ラクトンなど）を開環反応させて得られるポリエステルジオール化合物、あるいはジオール化合物（（ポリ）アルキレングリコール化合物、ビスフェノールなど）にオキシアルキレン（酸化エチレン、酸化プロピレンなど）やテトラヒドロフランなどを重付加させて得られるポリエーテルジオール化合物などが挙げられる。 Examples of the polyether polyol compound include a polyester diol compound obtained by ring-opening a cyclic ester compound (lactone, etc.), or a diol compound ((poly) alkylene glycol compound, bisphenol, etc.) and oxyalkylene (ethylene oxide, etc.). Examples thereof include polyether diol compounds obtained by heavy addition of (propylene oxide, etc.) and tetrahydrofuran, etc.
前記その他のポリオール化合物は、印刷層の耐油性や再溶解性を向上させる観点から、ポリエステルポリオール化合物が好ましい。前記ポリエステルポリオール化合物を使用する場合、前記ポリウレタン樹脂は、前記ポリオール由来の構造単位中、前記ポリテトラメチレンエーテルグリコール由来の構造単位と、ポリエステルポリオール化合物由来の構造単位の合計の割合が、７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。 The other polyol compound is preferably a polyester polyol compound from the viewpoint of improving the oil resistance and resolubility of the printed layer. When the polyester polyol compound is used, in the polyurethane resin, the total ratio of the structural unit derived from the polytetramethylene ether glycol and the structural unit derived from the polyester polyol compound to the structural unit derived from the polyol is 70% by mass. The above is preferable, 80% by mass or more is more preferable, and 90% by mass or more is further preferable.
前記その他のポリオール化合物の数平均分子量は、耐油性を向上させる観点から、２００以上が好ましく、４００以上がより好ましく、そして、２，０００以下が好ましく、１，０００以下がより好ましく、８００以下がさらに好ましい。なお、当該数平均分子量は、上述の式にて算出できる。 From the viewpoint of improving oil resistance, the number average molecular weight of the other polyol compounds is preferably 200 or more, more preferably 400 or more, preferably 2,000 or less, more preferably 1,000 or less, and preferably 800 or less. More preferred. The number average molecular weight can be calculated by the above formula.
前記鎖伸長剤は、分子内にイソシアネート基との反応可能な官能基（アミノ基、水酸基など）を２つ以上有する化合物が利用できる。分子内にアミノ基を２つ以上含有化合物としては、例えば、１級アミノ基を２つ有するジアミン類（エチレンジアミン、１，３−プロピレンジアミン、１，４−ブチレンジアミン、ヘキサメチレンジアミン、イソホロンジアミンなど）、１級アミノ基と２級アミノ基を１つずつ有するジアミン類（２−エチルアミノエチルアミンなど）、１級アミノ基を２つと２級アミノ基を１つ以上有するポリアミン類（ジエチレントリアミン、トリエチレンテトラミンなど）などが挙げられる。また、分子内に水酸基を２つ以上含有する水酸基含有化合物としては、低分子ジオール類（エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコールなど）などが挙げられる。さらに、分子内にアミノ基を２つと水酸基を１つ有する化合物としては、例えば、アミノエチルエタノールアミン、アミノプロピルエタノールアミンなど、上記１級アミノ基を２つ有するジアミン類にエチレンオキサイドの１モル付加物などが挙げられる。前記鎖伸長剤は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。 As the chain extender, a compound having two or more functional groups (amino group, hydroxyl group, etc.) capable of reacting with an isocyanate group in the molecule can be used. Examples of the compound containing two or more amino groups in the molecule include diamines having two primary amino groups (ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, isophoronediamine and the like. ), Diamines having one primary amino group and one secondary amino group (2-ethylaminoethylamine, etc.), polyamines having two primary amino groups and one or more secondary amino groups (diethylenetriamine, triethylene) (Tetramine, etc.) and the like. Examples of the hydroxyl group-containing compound containing two or more hydroxyl groups in the molecule include low-molecular-weight diols (ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.). Further, as a compound having two amino groups and one hydroxyl group in the molecule, for example, 1 mol of ethylene oxide is added to the above-mentioned diamines having two primary amino groups such as aminoethylethanolamine and aminopropylethanolamine. Things can be mentioned. At least one type of chain extender may be used, and two or more types may be used in combination.
前記鎖伸長剤は、ポリウレタン樹脂の分子内に水酸基やアミノ基などの官能基を導入する観点から、アミノ基、水酸基などの官能基を３つ以上有する化合物を用いることができる。前記アミノ基、水酸基などの官能基を３つ以上有する化合物としては、グリセリン、アミノエチルエタノールアミンなどが挙げられる。 As the chain extender, a compound having three or more functional groups such as an amino group and a hydroxyl group can be used from the viewpoint of introducing a functional group such as a hydroxyl group or an amino group into the molecule of the polyurethane resin. Examples of the compound having three or more functional groups such as an amino group and a hydroxyl group include glycerin and aminoethylethanolamine.
前記反応停止剤は、分子内にイソシアネート基との反応可能な官能基（アミノ基、水酸基など）を１つ以上有する化合物が利用でき、具体的には、モノアルコール類（メタノール、エタノールなど）、モノアミン類（ｎ−ブチルアミン、ジ−ｎ−ブチルアミンなど）、分子内にアミノ基と水酸基と１つずつ有するアルカノールアミン類（モノエタノールアミン、エチルエタノールアミン、ジエタノールアミン）などが挙げられる。また、前記反応停止剤としては、前記鎖伸長剤として挙げた化合物も利用できる。反応停止剤は、ポリウレタン樹脂の分子内に水酸基やアミノ基などの官能基を導入する観点から、前記分子内にアミノ基と水酸基と１つずつ有するアルカノールアミン類や、前記鎖伸長剤として例示した、１級アミノ基を２つ有するジアミン類や、低分子ジオール類を用いることができる。前記反応停止剤は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。 As the reaction terminator, a compound having at least one functional group (amino group, hydroxyl group, etc.) capable of reacting with an isocyanate group in the molecule can be used, and specifically, monoalcohols (methanol, ethanol, etc.), Examples thereof include monoamines (n-butylamine, di-n-butylamine, etc.) and alkanolamines (monoethanolamine, ethylethanolamine, diethanolamine) having one amino group and one hydroxyl group in the molecule. Further, as the reaction terminator, the compounds listed as the chain extender can also be used. The reaction terminator has been exemplified as an alkanolamine having one amino group and one hydroxyl group in the molecule and the chain extender from the viewpoint of introducing a functional group such as a hydroxyl group or an amino group into the molecule of the polyurethane resin. Diamines having two primary amino groups and low molecular weight diols can be used. At least one type of the reaction terminator may be used, and two or more types may be used in combination.
前記ジイソシアネート化合物とジオール化合物を反応させて得られるウレタンプレポリマーの製造において、ジイソシアネート化合物のＮＣＯとジオール化合物のＯＨの当量比（ジイソシアネート化合物のＮＣＯの当量／ジオール化合物のＯＨの当量）は、１．１〜３で反応させることが好ましく、１．２〜２で反応させることがより好ましい。 In the production of the urethane prepolymer obtained by reacting the diisocyanate compound with the diol compound, the equivalent ratio of NCO of the diisocyanate compound to OH of the diol compound (equivalent of NCO of the diisocyanate compound / equivalent of OH of the diol compound) is 1. The reaction is preferably 1 to 3 and more preferably 1.2 to 2.
前記鎖伸長剤は、前記プレポリマーの残存するイソシアネート基に対して、０．５〜０．９５当量程度の範囲で反応させることが好ましい。また、前記反応停止剤は、鎖伸長後のポリウレタン樹脂１モルに対して、１〜２モル程度の比率で反応させることが好ましい。 The chain extender preferably reacts with the remaining isocyanate groups of the prepolymer in the range of about 0.5 to 0.95 equivalents. Further, the reaction terminator is preferably reacted at a ratio of about 1 to 2 mol with respect to 1 mol of the polyurethane resin after chain extension.
前記ポリウレタン樹脂の重量平均分子量は、５，０００〜５０，０００であることが好ましく、１０，０００〜３０，０００であることがより好ましい。なお、本発明の重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）法によって測定することができる。一例として、ＧＰＣ装置としてＷａｔｅｒ２６９０（ウォーターズ社製）、カラムとしてＰＬｇｅｌ、５μ、ＭＩＸＥＤ−Ｄ（Ｐｏｌｙｍｅｒ Ｌａｂｏｒａｔｏｒｉｅｓ社製）を使用して、展開溶媒としてテトラヒドロフラン、カラム温度２５℃、流速１ミリリットル／分、ＲＩ検出器、試料注入濃度１０ミリグラム／ミリリットル、注入量１００マイクロリットルの条件下、クロマトグラフィーを行ない、ポリスチレン換算の重量平均分子量として求めることができる。 The weight average molecular weight of the polyurethane resin is preferably 5,000 to 50,000, more preferably 10,000 to 30,000. The weight average molecular weight of the present invention can be measured by a gel permeation chromatography (GPC) method. As an example, using Water2690 (manufactured by Waters) as a GPC apparatus, PLgel 5μ as a column, and MIXED-D (manufactured by Polymer Laboratories) as a developing solvent, tetrahydrofuran, column temperature 25 ° C., flow velocity 1 ml / min, RI. Chromatography can be performed under the conditions of a detector, a sample injection concentration of 10 mg / ml, and an injection amount of 100 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.
前記ポリウレタン樹脂は、水酸基やアミノ基などの官能基を有するポリウレタン樹脂が好ましい。このような官能基を有するポリウレタン樹脂を得る方法としては、上記のアミノ基、水酸基などの官能基を３つ以上有する化合物を鎖伸長剤として用いる方法や、前記鎖伸長剤や前記反応停止剤を用いずに、前記ジイソシアネート化合物を前記ジオール化合物の１．０倍未満のモル比率で反応させる方法などの既知の方法が採用できる。なお、前記ポリウレタン樹脂がアミノ基を有する場合、アミン価は０．１〜１０ｍｇＫＯＨ／ｇの範囲が好適である。前記アミン価は、固形分１ｇあたりのアミン価を意味し、０．１Ｎの塩酸水溶液を用い、電位差滴定法（例えば、ＣＯＭＴＩＴＥ（ＡＵＴＯ ＴＩＴＲＡＴＯＲ ＣＯＭ−９００、ＢＵＲＥＴ Ｂ−９００、ＴＩＴＳＴＡＴＩＯＮＫ−９００）、平沼産業社製）によって測定した後、水酸化カリウムの当量に換算して測定できる。 The polyurethane resin is preferably a polyurethane resin having a functional group such as a hydroxyl group or an amino group. As a method for obtaining a polyurethane resin having such a functional group, a method using the above-mentioned compound having three or more functional groups such as an amino group and a hydroxyl group as a chain extender, and the above-mentioned chain extender and the reaction terminator are used. A known method such as a method of reacting the diisocyanate compound at a molar ratio of less than 1.0 times that of the diol compound can be adopted without using the compound. When the polyurethane resin has an amino group, the amine value is preferably in the range of 0.1 to 10 mgKOH / g. The amine value means an amine value per 1 g of solid content, and a potential difference titration method (for example, COMITE (AUTO TITTOROR COM-900, BURET B-900, TITSATIONK-900), Hiranuma) is used using a 0.1 N hydrochloric acid aqueous solution. After measurement by Sangyo Co., Ltd.), it can be measured by converting it to the equivalent of potassium hydroxide.
＜セルロース誘導体＞
本発明のセルロース誘導体は、従来から表刷り用グラビア印刷インキ組成物に使用されるセルロース誘導体が使用でき、例えば、ニトロセルロースなどのニトロ基置換体；セルロースアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレートなどの低級アシル基置換体；メチルセルロース、エチルセルロースなどの低級アルキル置換体などが挙げられる。耐熱性を向上させる観点からは、ニトロ基置換体が好ましく、接着性を向上させる観点からは、低級アシル基置換体、低級アルキル置換体が好ましい。また、前記セルロース誘導体の水酸基の置換度は３０〜８５％程度が好ましい。前記セルロース誘導体は、２種以上を組み合わせて用いることができる。
<Cellulose derivative>
As the cellulose derivative of the present invention, a cellulose derivative conventionally used in a gravure printing ink composition for surface printing can be used. For example, a nitro group substituent such as nitrocellulose; cellulose acetate, cellulose acetate propionate, cellulose acetate butybean. Lower acyl group substituents such as rate; lower alkyl substituents such as methyl cellulose and ethyl cellulose can be mentioned. From the viewpoint of improving heat resistance, a nitro group substituted product is preferable, and from the viewpoint of improving adhesiveness, a lower acyl group substituted product and a lower alkyl substituted product are preferable. The degree of substitution of the hydroxyl group of the cellulose derivative is preferably about 30 to 85%. Two or more kinds of the cellulose derivatives can be used in combination.
＜塩化ビニル酢酸ビニル共重合体＞
本発明の塩化ビニル酢酸ビニル共重合体は、従来から表刷り用グラビア印刷インキ組成物に使用される塩化ビニルモノマーと酢酸ビニルモノマーを構成単位とする共重合体が使用できる。前記塩化ビニル酢酸ビニル共重合体は、２種以上を組み合わせて用いることができる。
<Vinyl chloride vinyl acetate copolymer>
As the vinyl chloride vinyl acetate copolymer of the present invention, a copolymer containing a vinyl chloride monomer and a vinyl acetate monomer, which have been conventionally used in a gravure printing ink composition for front printing, can be used. The vinyl chloride vinyl acetate copolymer can be used in combination of two or more.
前記塩化ビニル酢酸ビニル共重合体は、環境に配慮したインキの有機溶剤系において、インキの諸性能をバランスよく向上させるのに有利である観点から、水酸基を有する塩化ビニル酢酸ビニル共重合体が好ましい。前記水酸基を有する塩化ビニル酢酸ビニル共重合体は、酢酸エステル部分の一部をケン化することにより得ることができる。前記水酸基を有する塩化ビニル酢酸ビニル共重合体は、分子中の塩化ビニルモノマーの構成単位、酢酸ビニルモノマーの構成単位、およびケン化された酢酸ビニルモノマーの構成単位の比率によって、皮膜物性や溶解挙動が決定される。例えば、塩化ビニルモノマーの構成単位は樹脂皮膜の強靭さや硬さを付与し、酢酸ビニルモノマーの構成単位は接着性や柔軟性を付与し、ケン化された酢酸ビニルモノマーの構成単位は環境に配慮したインキの有機溶剤系への良好な溶解性を付与する。 The vinyl chloride vinyl acetate copolymer is preferably a vinyl chloride vinyl acetate copolymer having a hydroxyl group from the viewpoint of being advantageous in improving various performances of the ink in a well-balanced manner in an organic solvent system of an environment-friendly ink. .. The vinyl chloride vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a part of the acetate ester portion. The vinyl chloride vinyl acetate copolymer having a hydroxyl group has film physical properties and dissolution behavior depending on the ratio of the structural unit of the vinyl chloride monomer, the structural unit of the vinyl acetate monomer, and the structural unit of the saponified vinyl acetate monomer in the molecule. Is determined. For example, the constituent unit of the vinyl chloride monomer imparts the toughness and hardness of the resin film, the constituent unit of the vinyl acetate monomer imparts adhesiveness and flexibility, and the constituent unit of the saponified vinyl acetate monomer is environmentally friendly. It imparts good solubility of the vinyl chloride to the organic solvent system.
＜脂肪酸アミド＞
本発明の脂肪酸アミドは、従来から表刷り用グラビア印刷インキ組成物に使用される脂肪酸アミドが使用でき、例えば、飽和脂肪酸アミド、不飽和脂肪酸アミド、変性脂肪酸アミドなどが挙げられる。前記脂肪酸アミドは、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。
<Fatty acid amide>
As the fatty acid amide of the present invention, the fatty acid amide conventionally used in the gravure printing ink composition for front printing can be used, and examples thereof include saturated fatty acid amide, unsaturated fatty acid amide, and modified fatty acid amide. At least one type of fatty acid amide may be used, and two or more types may be used in combination.
＜有機溶媒＞
本発明の有機溶媒は、上記の成分を溶解あるいは分散されるものであれば、特に制限なく使用でき、例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ブタノールなどのアルコール系有機溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系有機溶媒；酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系有機溶媒；ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタンなどの脂肪族炭化水素系有機溶媒；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロヘプタン、シクロオクタンなどの脂環族炭化水素系有機溶媒；トルエン、キシレンなどの芳香族炭化水素系有機溶媒などが挙げられる。前記有機溶媒は、少なくとも１種を用いればよく、バインダー樹脂の溶解性や乾燥性などを考慮して、２種以上を組み合わせて用いることができる。環境に配慮する観点から、前記有機溶媒は、芳香族炭化水素系有機溶媒、ケトン系有機溶媒が、少量あるいは含まないほうが好ましい。
<Organic solvent>
The organic solvent of the present invention can be used without particular limitation as long as it dissolves or disperses the above components, and is, for example, an alcohol-based organic solvent such as methanol, ethanol, n-propanol, isopropanol, butanol; acetone, methyl ethyl ketone. , Ketone-based organic solvents such as methylisobutylketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, n-octane; Alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane; aromatic hydrocarbon-based organic solvents such as toluene and xylene can be mentioned. At least one type of the organic solvent may be used, and two or more types may be used in combination in consideration of the solubility and drying property of the binder resin. From the viewpoint of consideration for the environment, it is preferable that the organic solvent contains a small amount or no aromatic hydrocarbon-based organic solvent and ketone-based organic solvent.
以下に、本発明の表刷り用グラビア印刷インキ組成物に含まれる各成分の割合について説明する。 Hereinafter, the ratio of each component contained in the gravure printing ink composition for front printing of the present invention will be described.
前記顔料の割合は、前記表刷り用グラビア印刷インキ組成物中、０．５〜５０質量％であることが好ましく、５〜４０質量％であることがより好ましい。 The proportion of the pigment is preferably 0.5 to 50% by mass, more preferably 5 to 40% by mass in the gravure printing ink composition for front printing.
前記ポリウレタン樹脂の割合は、前記表刷り用グラビア印刷インキ組成物中、２〜３０質量％であることが好ましく、４〜１５質量％であることがより好ましい。 The proportion of the polyurethane resin is preferably 2 to 30% by mass, more preferably 4 to 15% by mass in the gravure printing ink composition for front printing.
前記セルロース誘導体及び／又は塩化ビニル酢酸ビニル共重合体の割合は、前記表刷り用グラビア印刷インキ組成物中、０．５〜１０質量％であることが好ましく、１〜５質量％であることがより好ましい。 The ratio of the cellulose derivative and / or the vinyl chloride vinyl acetate copolymer is preferably 0.5 to 10% by mass, and preferably 1 to 5% by mass in the gravure printing ink composition for front printing. More preferred.
前記脂肪酸アミドの割合は、前記表刷り用グラビア印刷インキ組成物中、０．１〜３質量％であることが好ましく、０．５〜２質量％であることがより好ましい。 The proportion of the fatty acid amide is preferably 0.1 to 3% by mass, more preferably 0.5 to 2% by mass in the gravure printing ink composition for front printing.
前記有機溶媒の割合は、前記表刷り用グラビア印刷インキ組成物中、インキの粘度を考慮して、１５〜９０質量％であることが好ましく、２５〜８０質量％であることがより好ましい。 The proportion of the organic solvent in the gravure printing ink composition for front printing is preferably 15 to 90% by mass, more preferably 25 to 80% by mass in consideration of the viscosity of the ink.
＜ハードレジン＞
本発明の表刷り用グラビア印刷インキ組成物には、接着性を向上させる観点から、ハードレジンを含有してもよい。前記ハードレジンとしては、例えば、ポリアミド樹脂、塩化ビニル酢酸ビニル共重合体、ダイマー酸系樹脂、ロジン系樹脂、マレイン酸系樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、ダンマル樹脂、コーパル樹脂、塩素化ポリプロピレン、酸化ポリプロピレンなどが挙げられる。前記ハードレジンは、２種以上を組み合わせて用いることができる。前記ハードレジンを使用する場合、前記ハードレジンの割合は、前記表刷り用グラビア印刷インキ組成物中、０．１〜５質量％であることが好ましく、０．５〜２．５質量％であることがより好ましい。
<Hard resin>
The gravure printing ink composition for front printing of the present invention may contain a hard resin from the viewpoint of improving adhesiveness. Examples of the hard resin include polyamide resin, vinyl chloride vinyl acetate copolymer, dimer acid resin, rosin resin, maleic acid resin, petroleum resin, terpene resin, ketone resin, dammar resin, copal resin, and chlorinated resin. Examples include polypropylene and polypropylene oxide. The hard resin can be used in combination of two or more. When the hard resin is used, the ratio of the hard resin is preferably 0.1 to 5% by mass, preferably 0.5 to 2.5% by mass, in the gravure printing ink composition for front printing. Is more preferable.
本発明の表刷り用グラビア印刷インキ組成物には、インキ組成物の性能が大幅に低下しない範囲でチタンキレート、ジルコニウムキレートなどの金属キレート架橋剤；ポリオレフィンワックス、パラフィンワックスなどのワックス類；レベリング剤、界面活性剤、可塑剤などを任意に添加することができる。 The gravure printing ink composition for surface printing of the present invention includes metal chelate cross-linking agents such as titanium chelate and zirconium chelate; waxes such as polyolefin wax and paraffin wax; leveling agents as long as the performance of the ink composition is not significantly deteriorated. , Surfactant, plasticizer and the like can be arbitrarily added.
＜表刷り用グラビア印刷インキ組成物の調製方法＞
本発明の表刷り用グラビア印刷インキ組成物を調製する方法としては、特に限定されず、例えば、上記の成分を順番に、あるいは同時に添加して、ビーズミル、ボールミル、サンドミル、アトライター、ロールミル、パールミル、高速攪拌装置、ペイントコンディショナーなどで混合して調製することができる。
<Preparation method of gravure printing ink composition for front printing>
The method for preparing the gravure printing ink composition for front printing of the present invention is not particularly limited, and for example, the above components are added in order or at the same time to a bead mill, a ball mill, a sand mill, an attritor, a roll mill, and a pearl mill. , Can be mixed with a high-speed stirrer, paint conditioner, etc.
＜印刷物＞
本発明の印刷物は、前記表刷り用グラビア印刷インキ組成物を基材（支持体）に塗工（印刷）し、乾燥することによって得られ、前記支持体上にインキ層（印刷皮膜）が形成されたものである。前記印刷の方法は、グラビア印刷機を用いることが好ましい。前記乾燥は、熱風などにより溶剤を蒸発させる工程を設けてもよい。前記印刷機による印刷条件は、従来公知の条件が適宜採用できる。
<Printed matter>
The printed matter of the present invention is obtained by applying (printing) the gravure printing ink composition for front printing on a base material (support) and drying it, and an ink layer (printing film) is formed on the support. It was done. It is preferable to use a gravure printing machine as the printing method. The drying may be provided with a step of evaporating the solvent with hot air or the like. As the printing conditions by the printing machine, conventionally known conditions can be appropriately adopted.
前記支持体（基材）としては、金属、木材、紙およびプラスチックのいずれでも良いが、これらの中でもプラスチックフィルムが好ましい。前記プラスチックフィルムとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル、ポリシクロオレフィン、ポリアセテート、ポリエーテルスルホン、ポリカーボネート、ポリアミド、ポリイミド、（メタ）アクリル系ポリマー、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリビニルアルコール、ポリアリレート、ポリフェニレンサルファイド、ジアセチルセルロースやトリアセチルセルロースなどのセルロース系ポリマーなどのフィルムが挙げられる。また、前記プラスチックフィルムは、防曇剤の塗工や練りこみなどがされた防曇フィルムであってもよい。 The support (base material) may be any of metal, wood, paper and plastic, but among these, a plastic film is preferable. Examples of the plastic film include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycycloolefin, polyacetate, polyether sulfone, polycarbonate, polyamide, polyimide, (meth) acrylic polymer, polyvinyl chloride, and polyvinylidene chloride. Examples thereof include films such as polystyrene, polyvinyl alcohol, polyarylate, polyphenylene sulfide, and cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose. Further, the plastic film may be an anti-fog film coated with an anti-fog agent or kneaded.
以下に本発明を実施例などによって説明するが、本発明はこれらのみに限定されない。 Hereinafter, the present invention will be described with reference to Examples and the like, but the present invention is not limited to these.
＜ポリウレタン樹脂の製造方法＞
＜ＰＵ−１の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量２，０００のポリテトラメチレンエーテルグリコール４００質量部、イソホロンジイソシアネート５７．７質量部、および触媒としてテトラブチルチタネート０．０４質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル８７１質量部、イソプロピルアルコール２１８質量部を加えた後、室温近くまで冷却し、イソホロンジアミン５．６質量部とアミノエチルエタノールアミン３．４質量部の混合物を加えて２０分間攪拌して、ＰＵ−１（固形分３０質量％）を得た。
<Manufacturing method of polyurethane resin>
<Manufacturing method of PU-1>
400 parts by mass of polytetramethylene ether glycol with a number average molecular weight of 2,000, 57.7 parts by mass of isophorone diisocyanate, and 0.04 tetrabutyl titanate as a catalyst in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. A mass portion was charged, and the reaction was carried out at 90 to 100 ° C. for 6 hours while introducing nitrogen gas. After adding 871 parts by mass of propyl acetate and 218 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 5.6 parts by mass of isophoronediamine and 3.4 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-1 (solid content 30% by mass) was obtained.
＜ＰＵ−２の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリテトラメチレンエーテルグリコール４００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−２（固形分３０質量％）を得た。
<Manufacturing method of PU-2>
400 parts by mass of polytetramethylene ether glycol with a number average molecular weight of 1,000, 115.4 parts by mass of isophorone diisocyanate, and 0.05 tetrabutyl titanate as a catalyst in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. A mass portion was charged, and the reaction was carried out at 90 to 100 ° C. for 6 hours while introducing nitrogen gas. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-2 (solid content 30% by mass) was obtained.
＜ＰＵ−３の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリテトラメチレングリコール２００質量部、３−メチル−１，５−ペンタンジオールとアジピン酸の縮合物である数平均分子量５００のポリエステルポリオール（商品名「クラポール」、クラレ社製）２００質量部、イソホロンジイソシアネート１７３．２質量部、および触媒としてテトラブチルチタネート０．０３質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル１１２０質量部、イソプロピルアルコール２８０質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１６．８質量部とアミノエチルエタノールアミン１０．３質量部の混合物を加えて２０分間攪拌して、ＰＵ−３（固形分３０質量％）を得た。
<Manufacturing method of PU-3>
A four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, containing 200 parts by mass of polytetramethylene glycol having a number average molecular weight of 1,000, and a condensate of 3-methyl-1,5-pentanediol and adipic acid. 200 parts by mass of polyester polyol (trade name "Kurapol", manufactured by Kuraray Co., Ltd.) having a number average molecular weight of 500, 173.2 parts by mass of isophorone diisocyanate, and 0.03 parts by mass of tetrabutyl titanate as a catalyst were charged, and while introducing nitrogen gas. The reaction was carried out at 90 to 100 ° C. for 6 hours. After adding 1120 parts by mass of propyl acetate and 280 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 16.8 parts by mass of isophorone diamine and 10.3 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-3 (solid content 30% by mass) was obtained.
＜ＰＵ−４の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリテトラメチレンエーテルグリコール２００質量部、３−メチル−１，５−ペンタンジオールとアジピン酸の縮合物である数平均分子量１，０００のポリエステルポリオール（商品名「クラポール」、クラレ社製）２００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−４（固形分３０質量％）を得た。
<Manufacturing method of PU-4>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 200 parts by mass of polytetramethylene ether glycol having a number average molecular weight of 1,000, a condensate of 3-methyl-1,5-pentanediol and adipic acid. 200 parts by mass of a certain number average molecular weight of 1,000 polyester polyol (trade name "Clapol", manufactured by Kuraray Co., Ltd.), 115.4 parts by mass of isophorone diisocyanate, and 0.05 parts by mass of tetrabutyl titanate as a catalyst are charged and nitrogen gas is charged. The reaction was carried out at 90 to 100 ° C. for 6 hours while introducing. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-4 (solid content 30% by mass) was obtained.
＜ＰＵ−５の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリテトラメチレンエーテルグリコール２００質量部、３−メチル−１，５−ペンタンジオールとアジピン酸の縮合物である数平均分子量２，０００のポリエステルポリオール（商品名「クラポール」、クラレ社製）２００質量部、イソホロンジイソシアネート８６．５８質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９３４質量部、イソプロピルアルコール２３３質量部を加えた後、室温近くまで冷却し、イソホロンジアミン８．４質量部とアミノエチルエタノールアミン５．１質量部の混合物を加えて２０分間攪拌して、ＰＵ−５（固形分３０質量％）を得た。
<Manufacturing method of PU-5>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 200 parts by mass of polytetramethylene ether glycol having a number average molecular weight of 1,000, a condensate of 3-methyl-1,5-pentanediol and adipic acid. A certain number average molecular weight of 2,000 polyester polyol (trade name "Clapol", manufactured by Claret) was charged with 200 parts by mass, isophorone diisocyanate by 86.58 parts by mass, and tetrabutyl titanate by 0.05 parts by mass as a catalyst, and nitrogen gas was charged. The reaction was carried out at 90 to 100 ° C. for 6 hours while introducing. After adding 934 parts by mass of propyl acetate and 233 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 8.4 parts by mass of isophoronediamine and 5.1 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-5 (solid content 30% by mass) was obtained.
＜ＰＵ−６の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリプロピレングリコール４００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−６（固形分３０質量％）を得た。
<Manufacturing method of PU-6>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 400 parts by mass of polypropylene glycol having a number average molecular weight of 1,000, 115.4 parts by mass of isophorone diisocyanate, and 0.05 parts by mass of tetrabutyl titanate as a catalyst were placed. The mixture was charged and reacted at 90 to 100 ° C. for 6 hours while introducing nitrogen gas. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-6 (solid content 30% by mass) was obtained.
＜ＰＵ−７の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに３−メチル−１，５−ペンタンジオールとアジピン酸の縮合物である数平均分子量１，０００のポリエステルポリオール（商品名「クラポール」、クラレ社製）４００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−７（固形分３０質量％）を得た。
<Manufacturing method of PU-7>
A polyester polyol with a number average molecular weight of 1,000, which is a condensate of 3-methyl-1,5-pentanediol and adipic acid, in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube (trade name "Clapol"). (Manufactured by Kuraray Co., Ltd.) 400 parts by mass, isophorone diisocyanate 115.4 parts by mass, and 0.05 parts by mass of tetrabutyl titanate as a catalyst were charged and reacted at 90 to 100 ° C. for 6 hours while introducing nitrogen gas. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-7 (solid content 30% by mass) was obtained.
＜ＰＵ−８の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリカプロラクトンジオール（商品名「プラクセル２１０」、ダイセル社製）４００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−８（固形分３０質量％）を得た。
<Manufacturing method of PU-8>
400 parts by mass of polycaprolactone diol (trade name "Plaxel 210", manufactured by Daicel Co., Ltd.) and isophorone diisocyanate 115.4 parts by mass in a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube. , And 0.05 parts by mass of tetrabutyl titanate as a catalyst, and the reaction was carried out at 90 to 100 ° C. for 6 hours while introducing nitrogen gas. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-8 (solid content 30% by mass) was obtained.
＜ＰＵ−９の製造方法＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに数平均分子量１，０００のポリプロピレングリコール２００質量部、３−メチル−１，５−ペンタンジオールとアジピン酸の縮合物である数平均分子量１０００のポリエステルポリオール（商品名「クラポール」、クラレ社製）２００質量部、イソホロンジイソシアネート１１５．４質量部、および触媒としてテトラブチルチタネート０．０５質量部を仕込み、窒素ガスを導入しながら９０〜１００℃で６時間反応させた。酢酸プロピル９９６質量部、イソプロピルアルコール２４９質量部を加えた後、室温近くまで冷却し、イソホロンジアミン１１．２質量部とアミノエチルエタノールアミン６．９質量部の混合物を加えて２０分間攪拌して、ＰＵ−９（固形分３０質量％）を得た。
<Manufacturing method of PU-9>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 200 parts by mass of polypropylene glycol having a number average molecular weight of 1,000, and a number average which is a condensate of 3-methyl-1,5-pentanediol and adipic acid. 200 parts by mass of polyester polyol (trade name "Kurapol", manufactured by Kuraray Co., Ltd.) having a molecular weight of 1000, 115.4 parts by mass of isophorone diisocyanate, and 0.05 parts by mass of tetrabutyl titanate as a catalyst were charged, and 90 to 90 parts were introduced while introducing nitrogen gas. The reaction was carried out at 100 ° C. for 6 hours. After adding 996 parts by mass of propyl acetate and 249 parts by mass of isopropyl alcohol, the mixture was cooled to near room temperature, a mixture of 11.2 parts by mass of isophorondiamine and 6.9 parts by mass of aminoethylethanolamine was added, and the mixture was stirred for 20 minutes. PU-9 (solid content 30% by mass) was obtained.
＜実施例、比較例＞
＜表刷り用グラビア印刷インキ組成物の調製＞
以下の表１に示される質量割合（質量％）にしたがって、それぞれの材料をペイントコンディショナーにて混練し、表刷り用グラビア印刷インキ組成物を調製した。得られた表刷り用グラビア印刷インキ組成物を混合溶媒（イソプロパノール：酢酸エチル：酢酸プロピル＝１：２：２）で希釈し、ザーンカップＮｏ．３で１５秒となるように調整し、印刷用の希釈インキを得た。この希釈インキについて、以下の条件にてグラビア印刷を行い、印刷物を得た。得られた印刷物について、以下の評価方法にしたがって、各項目を評価した。結果を表１に示す。
<Examples and comparative examples>
<Preparation of gravure printing ink composition for front printing>
Each material was kneaded with a paint conditioner according to the mass ratio (mass%) shown in Table 1 below to prepare a gravure printing ink composition for front printing. The obtained gravure printing ink composition for front printing was diluted with a mixed solvent (isopropanol: ethyl acetate: propyl acetate = 1: 2: 2) to obtain Zahn Cup No. The time was adjusted to 3 for 15 seconds to obtain a diluted ink for printing. Gravure printing was performed on this diluted ink under the following conditions to obtain a printed matter. Each item of the obtained printed matter was evaluated according to the following evaluation method. The results are shown in Table 1.
＜グラビア印刷条件＞
基材フィルム：防曇フィルムＭＶ２（２５μｍ、グンゼ社製）
印刷機械：グラビア校正機
インキを印刷する刷版：ヘリオ１７５ｉｎｅ／ｉｎｃｈ（図柄：ベタ印刷版）
印刷速度：８０ｍ／ｍｉｎ（通常速度）、１００ｍ／ｍｉｎ（高速時）
乾燥条件：８０℃
<Gravure printing conditions>
Base film: Anti-fog film MV2 (25 μm, manufactured by Gunze)
Printing machine: Gravure proofing machine Printing plate for printing ink: Helio 175ine / inch (Design: Solid printing plate)
Printing speed: 80 m / min (normal speed), 100 m / min (at high speed)
Drying conditions: 80 ° C
［耐アルコール性］
印刷物の印刷面をエタノールで浸した綿棒でこすり、印刷面の取れ具合から、以下の評価基準で耐アルコール性を評価した。
〇：５０回以上こすっても印刷面が取れないもの。
△：１０回〜４９回こすって印刷面が取れるもの。
×：１回〜９回こすって印刷面がとれるもの。
[Alcohol resistance]
The printed surface of the printed matter was rubbed with a cotton swab soaked in ethanol, and the alcohol resistance was evaluated according to the following evaluation criteria based on the degree of removal of the printed surface.
〇: The printed surface cannot be removed even after rubbing 50 times or more.
Δ: The printed surface can be removed by rubbing 10 to 49 times.
×: The printed surface can be removed by rubbing 1 to 9 times.
［防曇フィルムに対する耐ブロッキング性］
印刷物の印刷面と非印刷面を合わせて、バイスでしめこみ、４０℃で１日経過後に手で剥がし、インキの剥離の程度と剥離抵抗の強度から、以下の評価基準で防曇フィルムに対する耐ブロッキング性を評価した。
〇：印刷皮膜の剥離が全くない。
△：印刷皮膜が少し剥離し、剥離抵抗が強く感じられる。
×：印刷皮膜がほとんど剥離し、剥離抵抗が強く感じられる。
[Blocking resistance to anti-fog film]
Align the printed surface and the non-printed surface of the printed matter, squeeze it with a vise, and peel it off by hand after 1 day at 40 ° C. Based on the degree of ink peeling and the strength of peeling resistance, the resistance to anti-fog film is based on the following evaluation criteria. The blocking property was evaluated.
〇: There is no peeling of the printing film.
Δ: The print film is slightly peeled off, and the peeling resistance is strongly felt.
X: The print film is almost peeled off, and the peeling resistance is strongly felt.
本発明の表刷り用グラビア印刷インキ組成物は、上記の［耐アルコール性］および［防曇フィルムに対する耐ブロッキング性］において、×の評価がないものを合格基準とする。 In the gravure printing ink composition for front printing of the present invention, those having no evaluation of x in the above-mentioned [alcohol resistance] and [blocking resistance to antifogging film] are used as acceptance criteria.
以下、表刷り用グラビア印刷インキ組成物における、上記以外の評価について説明する。 Hereinafter, evaluations other than the above in the gravure printing ink composition for front printing will be described.
［インキの保存安定性］
上記で得られた各表刷り用グラビア印刷インキ組成物をガラス瓶に採取し、６０℃の雰囲気温度で１４日間保存した時の顔料の沈降の有無から、以下の評価基準でインキの保存安定性を評価した。
〇：沈降が見られず、インキの保存安定性は良好であった。
×：沈降が見られ、インキの保存安定性は不良であった。
[Ink storage stability]
The storage stability of the ink was determined by the following evaluation criteria based on the presence or absence of pigment settling when each of the gravure printing ink compositions for front printing obtained above was collected in a glass bottle and stored at an atmospheric temperature of 60 ° C. for 14 days. evaluated.
〇: No settling was observed, and the storage stability of the ink was good.
X: Sedimentation was observed, and the storage stability of the ink was poor.
［光沢性］
印刷物の光沢値をビックガードナー社製の光沢計を用いて入射角６０゜受光角６０°にして測定し、以下の評価基準で光沢性を評価した。
〇：光沢値が５０以上であり、非常に光沢があるもの。
△：光沢値が１０以上、５０未満であるもの。
×：光沢値が１０未満であるもの。
[Glossy]
The gloss value of the printed matter was measured using a gloss meter manufactured by Big Gardner with an incident angle of 60 ° and a light receiving angle of 60 °, and the glossiness was evaluated according to the following evaluation criteria.
〇: The gloss value is 50 or more, and it is very glossy.
Δ: The gloss value is 10 or more and less than 50.
X: The gloss value is less than 10.
［接着性］
印刷物の印刷面にセロハンテープを貼り付け、これを急速に剥がしたときの印刷皮膜がフィルムから剥離する度合いから、以下の評価基準で接着性を評価した。
〇：印刷皮膜の面積比率として、フィルムからの剥離が５％未満である。
△：印刷皮膜の面積比率として、５％以上３０％未満がフィルムから剥離する。
×：印刷皮膜の面積比率として、３０％以上がフィルムから剥離する。
[Adhesiveness]
Adhesiveness was evaluated according to the following evaluation criteria based on the degree to which the printed film peeled off from the film when the cellophane tape was attached to the printed surface of the printed matter and rapidly peeled off.
〇: As the area ratio of the printed film, the peeling from the film is less than 5%.
Δ: As the area ratio of the printed film, 5% or more and less than 30% is peeled from the film.
X: As the area ratio of the printing film, 30% or more is peeled from the film.
［耐熱性］
印刷物の印刷面に、８０〜２００℃の熱傾斜を有する熱板を備えたヒートシール試験機を用いて、印刷面とアルミ箔を２．０ｋｇ／ｃｍ２の圧力で１秒間押圧し、印刷面のインキがアルミ箔に転移する最低温度から、以下の評価基準で耐熱性を評価した。
〇：２００℃以上のもの。
△：１６０℃以上、２００℃未満のもの。
×：１６０℃未満のもの。
[Heat-resistant]
Using a heat seal tester equipped with a heat plate having a heat inclination of 80 to 200 ° C. on the printed surface of the printed matter, the printed surface and the aluminum foil are pressed at a pressure of 2.0 kg / cm2 for 1 second to cover the printed surface. The heat resistance was evaluated according to the following evaluation criteria from the lowest temperature at which the ink transferred to the aluminum foil.
〇: Those with a temperature of 200 ° C or higher.
Δ: Those having a temperature of 160 ° C or higher and lower than 200 ° C.
X: Those below 160 ° C.
［耐油性］
印刷物の印刷面を学振型耐摩擦試験機を用いて、サラダ油をしみ込ませたあて布で２００ｇの荷重下１００回摩擦し、印刷面の変化から、以下の評価基準で耐油性を評価した。
〇：印刷面に変化がないもの。
△：印刷面に筋状の傷が認められるもの。
×：印刷面に面状の傷が認められるもの。
[Oil resistance]
The printed surface of the printed matter was rubbed 100 times under a load of 200 g with a cloth impregnated with salad oil using a Gakushin type friction resistance tester, and the oil resistance was evaluated according to the following evaluation criteria based on the change in the printed surface.
〇: No change on the printed surface.
Δ: Streaks are found on the printed surface.
X: Surface scratches are found on the printed surface.
［延伸性］
印刷物を４００％まで引き延ばし、インキ受理層の剥離・破壊を以下の評価基準で延伸性を評価した。
〇：インキ皮膜の剥離・破壊が全くない。
×：インキ皮膜に剥離や破壊がある。
[Stretchability]
The printed matter was stretched to 400%, and the extensibility of peeling / breaking of the ink receiving layer was evaluated according to the following evaluation criteria.
〇: There is no peeling or destruction of the ink film.
X: There is peeling or breakage in the ink film.
［再溶解性］
印刷物を混合溶剤（イソプロパノール：酢酸エチル：酢酸プロピル＝１：２：２）中に浸漬し、インキ皮膜が全て溶出するまでの時間から、以下の評価基準で再溶解性を評価した。
〇：インキ皮膜が全て溶出するまで３０秒未満。
△：インキ皮膜が全て溶出するまで３０秒以上、６０秒未満。
×：インキ皮膜が全て溶出するまで６０秒以上かかるか、または溶出しない。
[Resolubility]
The printed matter was immersed in a mixed solvent (isopropanol: ethyl acetate: propyl acetate = 1: 2: 2), and the resolubility was evaluated according to the following evaluation criteria from the time until all the ink film was eluted.
〇: It takes less than 30 seconds for all the ink film to elute.
Δ: 30 seconds or more and less than 60 seconds until all the ink film is eluted.
X: It takes 60 seconds or more for all the ink film to elute, or does not elute.
［高速印刷適性］
ガイドロールの汚れから、以下の評価基準で高速印刷適性を評価した。
〇：ガイドロールに汚れが全く見られない。
△：ガイドロールに汚れがわずかに見られるが、実用レベルである。
×：ガイドロールに汚れが多く見られ、実用レベルにない。
[High-speed printing suitability]
The suitability for high-speed printing was evaluated based on the following evaluation criteria based on the stains on the guide roll.
〇: No dirt is seen on the guide roll.
Δ: The guide roll is slightly dirty, but it is at a practical level.
X: The guide roll is often dirty and is not at a practical level.
表1中、白色顔料は、酸化チタン；
藍色顔料は、Ｃ.Ｉ.ピグメントブルー１５：４；
セルロース誘導体は、ニトロセルロース（商品名「ＮＣ ＲＳ−２ ＫＣＮＣ」、ＫＯＲＥＡ ＣＮＣ ＬＴＤ社製）２０質量部を、酢酸プロピル３５質量部およびイソプロピルアルコール４５質量部からなる混合溶媒に溶解させた固形分２０質量％のニトロセルロース溶液；
塩化ビニル酢酸ビニル共重合体は、塩化ビニル酢酸ビニル共重合体（商品名「ソルバインＴＡ５Ｒ」、日信化学工業社製）２０質量部を、メチルエチルケトン４０質量部、酢酸エチル２０質量部、酢酸プロピル２０質量部からなる混合溶媒に溶解させた固形分２０質量％の塩化ビニル酢酸ビニル共重合体溶液；
脂肪酸アミドは、ラウリン酸アミド；
ハードレジンは、ロジン系樹脂（商品名「マルキードＮｏ．３」、荒川化学工業社製）；を示す。
In Table 1, the white pigment is titanium oxide;
The indigo pigment is CI Pigment Blue 15: 4;
The cellulose derivative has a solid content of 20 parts by mass of nitrocellulose (trade name "NC RS-2 KCNC", manufactured by KOREA CNC LTD) dissolved in a mixed solvent consisting of 35 parts by mass of propyl acetate and 45 parts by mass of isopropyl alcohol. Mass% nitrocellulose solution;
As the vinyl chloride vinyl acetate copolymer, 20 parts by mass of a vinyl chloride vinyl acetate copolymer (trade name "solvine TA5R", manufactured by Nisshin Kagaku Kogyo Co., Ltd.) is used, 40 parts by mass of methyl ethyl ketone, 20 parts by mass of ethyl acetate, and 20 parts by propyl acetate. A vinyl chloride vinyl acetate copolymer solution having a solid content of 20% by mass dissolved in a mixed solvent consisting of parts by mass;
Fatty acid amides are lauric acid amides;
The hard resin indicates a rosin-based resin (trade name “Marquid No. 3”, manufactured by Arakawa Chemical Industry Co., Ltd.);
実施例１〜７の結果から、本発明の表刷り用グラビア印刷インキ組成物は、耐アルコール性、および防曇フィルムに対する耐ブロッキング性を同時に発現できることが確認された。また、本発明の表刷り用グラビア印刷インキ組成物は、上記以外の評価（インキの保存安定性、光沢性、接着性、耐熱性、耐油性、延伸性、再溶解性、高速印刷適性）においても、良好な結果を示すことが確認された。 From the results of Examples 1 to 7, it was confirmed that the gravure printing ink composition for front printing of the present invention can simultaneously exhibit alcohol resistance and blocking resistance against an antifogging film. Further, the gravure printing ink composition for front printing of the present invention is evaluated in addition to the above (ink storage stability, glossiness, adhesiveness, heat resistance, oil resistance, stretchability, resolubility, high-speed printing suitability). Was also confirmed to show good results.
Claims (5)
前記ポリウレタン樹脂は、ポリオール由来の構造単位として、ポリテトラメチレンエーテルグリコール由来の構造単位を有することを特徴とする表刷り用グラビア印刷インキ組成物。 A gravure printing ink composition for surface printing containing a pigment, a polyurethane resin, a cellulose derivative and / or a vinyl chloride vinyl acetate copolymer, a fatty acid amide, and an organic solvent.
A gravure printing ink composition for surface printing, wherein the polyurethane resin has a structural unit derived from polytetramethylene ether glycol as a structural unit derived from polyol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019212881 | 2019-11-26 | ||
| JP2019212881 | 2019-11-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6786698B1 JP6786698B1 (en) | 2020-11-18 |
| JP2021088690A true JP2021088690A (en) | 2021-06-10 |
Family
ID=73220003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019226103A Active JP6786698B1 (en) | 2019-11-26 | 2019-12-16 | Gravure printing ink composition for front printing and printed matter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6786698B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102487809B1 (en) * | 2022-06-03 | 2023-01-13 | (주)성보잉크 | Alcohol type environment-freindly ink for surface printing of packing film and method of manufacturing the same |
| KR102509834B1 (en) * | 2022-12-07 | 2023-03-14 | 일광잉크페인트(주) | Non-toxic and environmental-friendly ink composition for gravure print |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6861877B1 (en) * | 2020-08-21 | 2021-04-21 | サカタインクス株式会社 | Gravure printing ink composition for front printing and printed matter |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009119800A1 (en) * | 2008-03-28 | 2009-10-01 | 日清食品ホールディングス株式会社 | Ink composition for printing, paper container material using the ink composition, and heat insulating foamed paper container |
| JP2017039896A (en) * | 2015-08-21 | 2017-02-23 | サカタインクス株式会社 | Gravure printing ink composition for surface printing and surface printing gravure printed matter printed therewith |
| JP2018053014A (en) * | 2016-09-27 | 2018-04-05 | 東洋インキＳｃホールディングス株式会社 | Gravure ink and printed matter |
| JP2018058979A (en) * | 2016-10-04 | 2018-04-12 | サカタインクス株式会社 | Gravure printing ink composition for surface printing |
| WO2018110408A1 (en) * | 2016-12-16 | 2018-06-21 | Ｄｉｃグラフィックス株式会社 | Laminate ink composition for flexible packaging |
| JP2018123333A (en) * | 2018-03-27 | 2018-08-09 | 東洋インキＳｃホールディングス株式会社 | Gravure ink and printed matter |
| JP2018188558A (en) * | 2017-05-08 | 2018-11-29 | サカタインクス株式会社 | Gravure printing ink composition for surface printing |
| JP2019089941A (en) * | 2017-11-15 | 2019-06-13 | 東洋インキＳｃホールディングス株式会社 | Gravure ink for surface printing and printed matter of the same |
| JP2019112583A (en) * | 2017-12-26 | 2019-07-11 | 東洋インキＳｃホールディングス株式会社 | Ink set and decorative material |
| JP2019123810A (en) * | 2018-01-17 | 2019-07-25 | Ｄｉｃグラフィックス株式会社 | Liquid ink composition |
-
2019
- 2019-12-16 JP JP2019226103A patent/JP6786698B1/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009119800A1 (en) * | 2008-03-28 | 2009-10-01 | 日清食品ホールディングス株式会社 | Ink composition for printing, paper container material using the ink composition, and heat insulating foamed paper container |
| JP2017039896A (en) * | 2015-08-21 | 2017-02-23 | サカタインクス株式会社 | Gravure printing ink composition for surface printing and surface printing gravure printed matter printed therewith |
| JP2018053014A (en) * | 2016-09-27 | 2018-04-05 | 東洋インキＳｃホールディングス株式会社 | Gravure ink and printed matter |
| JP2018058979A (en) * | 2016-10-04 | 2018-04-12 | サカタインクス株式会社 | Gravure printing ink composition for surface printing |
| WO2018110408A1 (en) * | 2016-12-16 | 2018-06-21 | Ｄｉｃグラフィックス株式会社 | Laminate ink composition for flexible packaging |
| JP2018188558A (en) * | 2017-05-08 | 2018-11-29 | サカタインクス株式会社 | Gravure printing ink composition for surface printing |
| JP2019089941A (en) * | 2017-11-15 | 2019-06-13 | 東洋インキＳｃホールディングス株式会社 | Gravure ink for surface printing and printed matter of the same |
| JP2019112583A (en) * | 2017-12-26 | 2019-07-11 | 東洋インキＳｃホールディングス株式会社 | Ink set and decorative material |
| JP2019123810A (en) * | 2018-01-17 | 2019-07-25 | Ｄｉｃグラフィックス株式会社 | Liquid ink composition |
| JP2018123333A (en) * | 2018-03-27 | 2018-08-09 | 東洋インキＳｃホールディングス株式会社 | Gravure ink and printed matter |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102487809B1 (en) * | 2022-06-03 | 2023-01-13 | (주)성보잉크 | Alcohol type environment-freindly ink for surface printing of packing film and method of manufacturing the same |
| KR102509834B1 (en) * | 2022-12-07 | 2023-03-14 | 일광잉크페인트(주) | Non-toxic and environmental-friendly ink composition for gravure print |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6786698B1 (en) | 2020-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6636483B2 (en) | Printing ink composition for lamination for flexible packaging | |
| JP6632251B2 (en) | Gravure printing ink composition for front printing and front printing gravure printed matter | |
| JP6786698B1 (en) | Gravure printing ink composition for front printing and printed matter | |
| JP6299765B2 (en) | Binder for printing ink, laminate ink composition for soft packaging, and printed matter | |
| JP6363866B2 (en) | Gravure printing ink composition for surface printing | |
| CA2877846C (en) | Alcohol-based printing ink composition | |
| JP7217769B2 (en) | Gravure printing ink composition for surface printing | |
| JP2016196560A (en) | Gravure printing ink composition for surface printing | |
| JP6666324B2 (en) | Printing ink composition for lamination for flexible packaging | |
| JP2017025256A (en) | Gravure printing ink composition for surface printing and surface-printed gravure printed matter | |
| JP5728749B1 (en) | Printing ink | |
| JP6585350B2 (en) | Printing ink composition for shrink packaging and printed matter for shrink packaging | |
| JP6915976B2 (en) | Gravure printing ink composition for front printing | |
| JP6339891B2 (en) | Surface print gravure | |
| JP6861877B1 (en) | Gravure printing ink composition for front printing and printed matter | |
| JP2010270216A (en) | Binder for printing ink | |
| JP2020183489A (en) | Binder for printing ink and printing ink using the same | |
| JP3471087B2 (en) | Aqueous printing ink composition for lamination | |
| JP7245952B1 (en) | Gravure printing ink composition for surface printing | |
| JP6992925B1 (en) | Gravure printing ink for front printing, printed matter using it | |
| JP2002226755A (en) | Printing ink composition | |
| JPH1060259A (en) | Cold-curable water-based polyurethane resin composition and its use | |
| JP4973130B2 (en) | Composition for printing ink | |
| JP2001098046A (en) | Polyurethane urea and its use | |
| WO2021106367A1 (en) | Printing ink composition for laminate for flexible packaging |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191224 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20191224 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20200107 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200214 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200313 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200324 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200623 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200819 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20200901 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200917 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20200917 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20200930 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20201001 |
|
| 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: 20201020 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201028 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6786698 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |