JP6674771B2 - Method for producing laminate ink composition for ultraviolet shielding soft packaging - Google Patents
Method for producing laminate ink composition for ultraviolet shielding soft packaging Download PDFInfo
- Publication number
- JP6674771B2 JP6674771B2 JP2015243247A JP2015243247A JP6674771B2 JP 6674771 B2 JP6674771 B2 JP 6674771B2 JP 2015243247 A JP2015243247 A JP 2015243247A JP 2015243247 A JP2015243247 A JP 2015243247A JP 6674771 B2 JP6674771 B2 JP 6674771B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- ultraviolet shielding
- ink composition
- ink
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 238000004806 packaging method and process Methods 0.000 title claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 138
- 239000011787 zinc oxide Substances 0.000 claims description 69
- 229920005749 polyurethane resin Polymers 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 229940008099 dimethicone Drugs 0.000 claims description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 27
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 27
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 27
- 238000009459 flexible packaging Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 235000013372 meat Nutrition 0.000 claims description 12
- 229920006026 co-polymeric resin Polymers 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002635 aromatic organic solvent Substances 0.000 claims description 6
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000010008 shearing Methods 0.000 claims 1
- 239000000976 ink Substances 0.000 description 104
- 235000014692 zinc oxide Nutrition 0.000 description 67
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
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- 150000002431 hydrogen Chemical class 0.000 description 26
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- 239000002245 particle Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010030 laminating Methods 0.000 description 12
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
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- 239000011324 bead Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- CBJHPWGNQLOEPT-UHFFFAOYSA-N ethenyl acetate Chemical compound CC(=O)OC=C.CC(=O)OC=C CBJHPWGNQLOEPT-UHFFFAOYSA-N 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 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 4
- 239000002981 blocking agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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- 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
- PXIPZIPSDBXFQR-UHFFFAOYSA-N 4,5-dimethyloxolan-2-one Chemical compound CC1CC(=O)OC1C PXIPZIPSDBXFQR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 1
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- WRQJLHLZXPOHBW-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(CCl)(CCl)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(CCl)(CCl)C1=CC=CC=C1 WRQJLHLZXPOHBW-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
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- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ADANNTOYRVPQLJ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-[[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilyl]oxy-dimethylsilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C ADANNTOYRVPQLJ-UHFFFAOYSA-N 0.000 description 1
- QUFSNPAIQDHOSV-UHFFFAOYSA-N acetic acid chloroethene ethenyl acetate Chemical compound ClC=C.CC(O)=O.CC(=O)OC=C QUFSNPAIQDHOSV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PROZFBRPPCAADD-UHFFFAOYSA-N ethenyl but-3-enoate Chemical compound C=CCC(=O)OC=C PROZFBRPPCAADD-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 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 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 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
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940008424 tetradecamethylhexasiloxane Drugs 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Wrappers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、各種食品、化粧品、点滴用調剤、アンプル、注射器等の医薬品の軟包装フィルムパッケージ材に用いる紫外線遮蔽軟包装用ラミネートインキの製造方法に関する。詳しくは、中身が透けて見えて、尚且つ紫外線を遮断するフィルムパッケージに用いる紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。 The present invention relates to a method for producing a laminate ink for ultraviolet shielding soft packaging used for a soft packaging film packaging material for pharmaceuticals such as various foods, cosmetics, infusion preparations, ampules, syringes and the like. More specifically, the present invention relates to a method for producing a laminated ink composition for soft UV shielding used in a film package that allows the contents to be seen through and that blocks UV rays.
食品、医薬品等の包装パッケージには、紫外線による内容物の劣化を防ぐためにアルミ蒸着フィルムを用いることが多いが、中身が一目で確認できる安心・安全の観点から、内容物が見えて尚且つ紫外線を遮断するフィルムパッケージの要求が出てきている。
一方で、酸化亜鉛は紫外線を吸収し、他顔料に比べ透明度を有することから、紫外線遮蔽効果のある酸化亜鉛を用いた紫外線遮蔽コーティング組成物の発明が成されている（例えば、特開２０１１−２５２１２０）。
しかし、市場では更なる透明性を有し、尚且つ紫外線遮蔽率の高いフィルムが要求されている。酸化亜鉛を微粒子化することにより、フィルム塗布時の透明度が向上するが、現行の分散練肉による製造方法では透明度に限界がある。また、酸化亜鉛の添加量を変化させることにより透明度も変動するが、紫外線遮蔽率は酸化亜鉛の含有量が下がると劣る傾向にあり、透明性と紫外線遮蔽率の両立が望まれる。本発明は、現状のフィルムへの密着性、塗膜のスクラッチ性と言った基本性能に加えて、高い遮断性を保持しつつ、可視光に対してより透明性の高い包材用途向けフィルムパッケージに用いる紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関するものである。
Aluminum and aluminum vapor-deposited films are often used for packaging of foods and pharmaceuticals to prevent deterioration of the contents due to ultraviolet rays. However, from the viewpoint of safety and security that the contents can be checked at a glance, the contents are visible and There is a demand for a film package that shuts off the air.
On the other hand, since zinc oxide absorbs ultraviolet light and has transparency compared to other pigments, an invention of an ultraviolet shielding coating composition using zinc oxide having an ultraviolet shielding effect has been made (for example, JP-A-2011-2011). 252120).
However, in the market, there is a demand for a film having further transparency and a high ultraviolet ray shielding rate. By making zinc oxide into fine particles, the transparency at the time of film application is improved, but there is a limit to the transparency in the current production method using dispersed meat. The transparency also varies with the amount of zinc oxide added, but the ultraviolet shielding factor tends to be inferior when the zinc oxide content decreases, and it is desired to achieve both transparency and ultraviolet shielding factor. The present invention provides a film package for packaging materials that is more transparent to visible light while maintaining high barrier properties, in addition to the basic properties such as the current adhesion to a film and the scratch property of a coating film. The present invention relates to a method for producing a laminating ink composition for ultraviolet shielding flexible packaging used in the present invention.
本発明は、フィルムへの密着性、塗膜のスクラッチ性と言った基本性能に加えて、紫外線に対しては高い遮断性を保持しつつ、可視光に対してはより高い透明性を持つ食品、化粧品、医薬品等の包材用途向けフィルムパッケージに用いる紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。 The present invention provides a food product having higher transparency to visible light while maintaining high blocking properties against ultraviolet rays, in addition to basic properties such as adhesion to a film and scratching properties of a coating film. The present invention relates to a method for producing a laminating ink composition for ultraviolet shielding flexible packaging used in a film package for packaging materials such as cosmetics, pharmaceuticals and pharmaceuticals.
本発明者らは、前記した課題を解決するために鋭意研究を重ねた結果、ポリウレタン樹脂、塩酢ビニル酢酸ビニル共重合樹脂、ハイドロゲンジメチコン処理した酸化亜鉛、無処理酸化亜鉛、及び芳香有機溶剤を除く有機溶剤の混合物に対する練肉方法を工夫することで、課題解決に有効であることを見出した。 The present inventors have conducted intensive studies to solve the above-described problems, and as a result, a polyurethane resin, a vinyl acetate vinyl acetate copolymer resin, a zinc oxide treated with hydrogen dimethicone, an untreated zinc oxide, and an aromatic organic solvent. By devising a meat mixing method for a mixture of organic solvents to be removed, it has been found that it is effective in solving the problem.
即ち、本発明は、ポリウレタン樹脂、塩酢ビニル酢酸ビニル共重合樹脂、ハイドロゲンジメチコン処理した酸化亜鉛、無処理酸化亜鉛、及び芳香有機溶剤を除く有機溶剤の混合物を、高せん断力を与えることで練肉、分散した後小片化させることを特徴とする紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。
また、本発明は、高せん断力を与える手段として、２本ロール練肉機を用いる請求項１に記載の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。
また、本発明は、使用するポリウレタン樹脂の重量平均分子量が１５，０００〜１００，０００、ガラス転移点（Ｔｇ）−４５〜−１０℃、である紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。
加えて、本発明は、使用する塩酢ビニル酢酸ビニル共重合樹脂の水酸基価が、５０〜２００ｍｇＫＯＨ／ｇであり、且つ共重合体樹脂中の塩化ビニル成分の含有率が８０〜９５質量部である紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する。
That is, the present invention kneads a mixture of a polyurethane resin, a vinyl acetate vinyl acetate copolymer resin, zinc oxide treated with hydrogen dimethicone, untreated zinc oxide, and an organic solvent excluding an aromatic organic solvent by applying a high shear force. The present invention relates to a method for producing a laminating ink composition for ultraviolet shielding soft packaging, characterized in that the meat is dispersed and then fragmented.
The present invention also relates to the method for producing a laminate ink composition for ultraviolet shielding flexible packaging according to claim 1, wherein a two-roll mill is used as a means for giving a high shear force.
Further, the present invention provides a method for producing a laminated ink composition for ultraviolet shielding flexible packaging, wherein the polyurethane resin used has a weight average molecular weight of 15,000 to 100,000 and a glass transition point (Tg) of 45 to -10 ° C. About.
In addition, according to the present invention, the vinyl acetate vinyl acetate copolymer used has a hydroxyl value of 50 to 200 mgKOH / g, and the content of the vinyl chloride component in the copolymer resin is 80 to 95 parts by mass. The present invention relates to a method for producing a laminate ink composition for a soft ultraviolet shielding soft packaging.
従来は、高い紫外線遮蔽性を保持すると可視光の透明性が低下してしまうのに対し、本発明により、フィルムへの密着性、塗膜のスクラッチ性と言った基本性能に加えて、紫外線に対しては高い遮断性を保持しつつ、可視光に対してはより高い透明性を持つフィルムパッケージ向け紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法を提供する。 Conventionally, if high UV shielding properties are maintained, the transparency of visible light will be reduced.On the other hand, according to the present invention, in addition to basic performance such as adhesion to films and scratch resistance of coating films, ultraviolet rays Provided is a method for producing a laminating ink composition for ultraviolet shielding soft packaging for a film package having higher transparency to visible light while maintaining high shielding properties.
本発明について詳細に説明する。なお以下の説明で用いる「インキ組成物」とは全て「紫外線遮蔽軟包装用ラミネートインキ組成物」を示す。また「部」とは全て「質量部」を示す。 The present invention will be described in detail. The term “ink composition” used in the following description refers to “laminate ink composition for ultraviolet shielding soft packaging”. In addition, all “parts” indicate “parts by mass”.
本発明は、ポリウレタン樹脂、塩酢ビニル酢酸ビニル共重合樹脂、ハイドロゲンジメチコン処理した酸化亜鉛、無処理酸化亜鉛、及び芳香有機溶剤を除く有機溶剤の混合物を、高せん断力を与えることで練肉、分散した後小片化させることを特徴とする紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法に関する発明である。 The present invention provides a mixture of a polyurethane resin, a vinyl acetate vinyl acetate copolymer resin, a hydrogen dimethicone-treated zinc oxide, an untreated zinc oxide, and a mixture of organic solvents excluding an aromatic organic solvent, by applying a high shear force to the meat, The present invention relates to a method for producing a laminated ink composition for ultraviolet shielding soft packaging, which is characterized by dispersing and then fragmenting.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法では、具体的には前記ポリウレタン樹脂、塩酢ビニル酢酸ビニル共重合樹脂、ハイドロゲンジメチコン処理した酸化亜鉛、無処理酸化亜鉛、及び芳香有機溶剤を除く有機溶剤の混合物を、高せん断力を与えることで練肉、分散した後小片化させたチップ配合物であるインキ組成物を予め作製し、このチップ配合物に更にウレタン樹脂、酢酸エチル、イソプロピルアルコール、ノルマルプロピルアセテート、メチルエチルケトンなど各種有機溶剤に溶解させ、消泡剤等各種添加剤を添加し練肉することで十分分散された紫外線遮蔽軟包装用ラミネートインキを得ることができる。 In the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention, specifically, the polyurethane resin, vinyl acetate vinyl acetate copolymer resin, hydrogen dimethicone-treated zinc oxide, untreated zinc oxide, and an aromatic organic solvent The mixture of organic solvents except for, by applying a high shear force, kneaded, prepared beforehand an ink composition that is a chip composition was dispersed and fragmented, urethane resin, ethyl acetate, further this chip composition By dissolving in various organic solvents such as isopropyl alcohol, normal propyl acetate, and methyl ethyl ketone, adding various additives such as an antifoaming agent, and kneading the mixture, a sufficiently dispersed ultraviolet shielding soft packaging laminate ink can be obtained.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用するポリウレタン樹脂は、ポリエーテルポリオールを原料とするポリウレタン樹脂であり、ポリエーテルポリオールの含有比率が、ポリウレタン樹脂１００質量部に対して、数平均分子量１００〜３５００のポリエーテルポリオールが１〜３０質量部の範囲であることが好ましい。詳細は後述するが、ポリエーテルポリオール樹脂としては、酸化エチレン、酸化プロピレン、テトラヒドロフランなどの重合体または共重合体のポリエーテルポリオール類が挙げられる。具体的には、ポリエチレングリコール樹脂、ポリプロピレングリコール樹脂、ポリテトラメチレングリコール樹脂など公知汎用のものでよい。ポリエーテル樹脂を上記の範囲で含有することにより、特にフィルムへの密着性が大幅に向上し、結果として耐ブロッキング性、ラミネート強度が優れるようになる。
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用するポリウレタン樹脂の構成成分であるポリエーテルポリオール樹脂の数平均分子量が１００より小さいと、ポリウレタン樹脂の皮膜が硬くなる傾向にあり、特にポリエステルフィルムへの接着性が悪くなる。数平均分子量が３５００より大きい場合、ポリウレタン樹脂の皮膜が脆弱になる傾向にありインキ皮膜の耐ブロッキング性が悪くなる。ポリウレタン樹脂１００質量部に対してポリエーテルポリオールの比率が１質量部未満であると、該ウレタン樹脂のケトン、エステル、アルコール系溶剤への溶解性が悪くなる。またインキ皮膜の該溶剤への再溶解性が悪くなり、印刷物の調子再現性が劣る。また３０質量部を超えると、耐ブロッキングが劣る傾向がある。
The polyurethane resin used in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention is a polyurethane resin using polyether polyol as a raw material, and the content ratio of the polyether polyol is based on 100 parts by mass of the polyurethane resin. The amount of the polyether polyol having a number average molecular weight of 100 to 3500 is preferably in the range of 1 to 30 parts by mass. Although details will be described later, examples of the polyether polyol resin include polyether polyols of a polymer or a copolymer such as ethylene oxide, propylene oxide, and tetrahydrofuran. Specifically, known general-purpose resins such as polyethylene glycol resin, polypropylene glycol resin, and polytetramethylene glycol resin may be used. When the polyether resin is contained in the above range, adhesion to a film is particularly greatly improved, and as a result, blocking resistance and lamination strength are improved.
When the number average molecular weight of the polyether polyol resin, which is a component of the polyurethane resin used in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention, is less than 100, the polyurethane resin film tends to be hard, In particular, the adhesion to the polyester film is poor. When the number average molecular weight is more than 3500, the polyurethane resin film tends to be brittle and the ink film has poor blocking resistance. When the ratio of the polyether polyol is less than 1 part by mass with respect to 100 parts by mass of the polyurethane resin, the solubility of the urethane resin in ketone, ester, and alcohol-based solvents becomes poor. Further, the resolubility of the ink film in the solvent becomes poor, and the tone reproducibility of the printed matter is poor. If it exceeds 30 parts by mass, the blocking resistance tends to be poor.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用するポリウレタン樹脂に必要に応じて使用される併用ポリオールとしては、ポリウレタン樹脂の製造に一般的に用いられる各種公知のポリオールを用いることができ、１種または２種以上を併用してもよい。例えば、酸化メチレン、酸化エチレン、テトラヒドロフランなどの重合体または共重合体のポリエーテルポリオール類（１）；エチレングリコール、１，２―プロパンジオール、１，３―プロパンジオール、２メチル−１，３プロパンジオール、２エチル−２ブチル−１，３プロパンジオール、１，３―ブタンジオール、１，４―ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３−メチル−１，５ペンタンジオール、ヘキサンジオール、オクタンジオール、１，４−ブチンジオール、１，４―ブチレンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、１，２，６−ヘキサントリオール、１，２，４−ブタントリオール、ソルビトール、ペンタエスリトールなどの飽和または不飽和の低分子ポリオール類（２）；これらの低分子ポリオール類（２）と、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、こはく酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、トリメリット酸、ピロメリット酸などの多価カルボン酸あるいはこれらの無水物とを脱水縮合または重合させて得られるポリエステルポリオール類（３）；環状エステル化合物、例えばポリカプロラクトン、ポリバレロラクトン、ポリ（β−メチル−γ−バレロラクトン）等のラクトン類、を開環重合して得られるポリエステルポリオール類（４）；前記低分子ポリオール類（２）などと、例えばジメチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲン等との反応によって得られるポリカーボネートポリオール類（５）；ポリブタジエングリコール類（６）；ビスフェノールＡに酸化エチレンまたは酸化プロピレンを付加して得られるグリコール類（７）；１分子中に１個以上のヒドロキシエチル、アクリル酸ヒドロキシプロプル、アクリルヒドロキシブチル等、或いはこれらの対応するメタクリル酸誘導体等と、例えばアクリル酸、メタクリル酸又はそのエステルとを共重合することによって得られるアクリルポリオール（８）などが挙げられる。 As a combined polyol used as necessary for the polyurethane resin used in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention, various known polyols generally used for producing a polyurethane resin may be used. May be used alone or in combination of two or more. For example, polymer or copolymer polyether polyols (1) such as methylene oxide, ethylene oxide, and tetrahydrofuran; ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propane Diol, 2ethyl-2butyl-1,3propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5 pentanediol, hexanediol, octanediol 1,4-butynediol, 1,4-butylene diol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4- Butanetriol, Saturated or unsaturated low molecular weight polyols (2) such as rubitol and pentaethritol; these low molecular weight polyols (2) and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, Dehydration condensation or polymerization of polycarboxylic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid, and pyromellitic acid, or anhydrides thereof. Polyester polyols (3) obtained; ring-opening polymerization of cyclic ester compounds such as lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone); ); Low molecular polyols (2) and the like, for example, dimethyl carbonate, diphenyl Polycarbonate polyols (5) obtained by reaction with carbonate, ethylene carbonate, phosgene, etc .; Polybutadiene glycols (6); Glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (7); Acrylic polyol obtained by copolymerizing at least one of hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl and the like, or their corresponding methacrylic acid derivatives with acrylic acid, methacrylic acid or an ester thereof (8) and the like.
なお、前記ポリエステルポリオール類（３）のなかで、ジオール類（グリコール類）と二塩基酸とから得られる高分子ジオールは、ジオール類のうち５モル％までを前記水酸基を３つ以上有する低分子ポリオール類（２）に置換することが出来る。 Among the polyester polyols (3), a high molecular weight diol obtained from a diol (glycol) and a dibasic acid is a low molecular weight compound having up to 5 mol% of the diols having three or more of the hydroxyl groups. It can be replaced by polyols (2).
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法におけるポリウレタン樹脂に使用されるジイソシアネート化合物としては、ポリウレタン樹脂の製造に一般的に用いられる各種公知の芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートなどが挙げられる。例えば、１，５―ナフチレンジイソシアネート、４，４’―ジフェニルメタンジイソシアネート、４，４’―ジフェニルジメチルメタンジイソシアネート、４，４’―ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３―フェニレンジイソシアネート、１，４―フェニレンジイソシアネート、トリレンジイソシアネート、ブタン―１，４―ジイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、２，２，４―トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサン―１，４―ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジメリールジイソシアネート、ジシクロヘキシルメタン―４，４’―ジイソシアネート、１，３―ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ノルボルナンジイソシアネート、ｍーテトラメチルキシリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ビス−クロロメチル−ジフェニルメタン−ジイソシアネート、２，６−ジイソシアネート−ベンジルクロライドやダイマー酸のカルボキシル基をイソシアネート基に転化したダイマージイソシアネート等があげられる。これらのジイソシアネート化合物は単独で、または２種以上を混合して用いることができる。 Examples of the diisocyanate compound used for the polyurethane resin in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic rings generally used for producing polyurethane resins. Group diisocyanate and the like. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1 , 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, Meryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate And bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and dimer isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These diisocyanate compounds can be used alone or in combination of two or more.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法におけるポリウレタン樹脂に使用される鎖伸長剤としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、ジシクロヘキシルメタン―４，４’―ジアミンなどの他、２―ヒドロキシエチルエチレンジアミン、２―ヒドロキシエチルプロピルジアミン、２―ヒドロキシエチルプロピレンジアミン、ジ―２―ヒドロキシエチルエチレンジアミン、ジ―２―ヒドロキシエチレンジアミン、ジ―２―ヒドロキシエチルプロピレンジアミン、２―ヒドロキシピロピルエチレンジアミン、ジ―２―ヒドロキシピロピルエチレンジアミン、ジ―２―ヒドロキシプロピルエチレンジアミンなど分子内に水酸基を有するアミン類も用いることが出来る。これらの鎖伸長剤は単独で、または２種以上を混合して用いることができる。
また、反応停止を目的とした末端封鎖剤として、一価の活性水素化合物を用いることもできる。かかる化合物としてはたとえば、ジーｎーブチルアミン等のジアルキルアミン類やエタノール、イソプロピルアルコール等のアルコール類があげられる。更に、特にポリウレタン樹脂中にカルボキシル基を導入したいときには、グリシン、Ｌ−アラニン等のアミノ酸を反応停止剤として用いることができる。これらの末端封鎖剤は単独で、または２種以上を混合して用いることができる。
Examples of the chain extender used for the polyurethane resin in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4. , 4'-diamine and the like, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethyl In the molecule such as propylene diamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, di-2-hydroxypropylethylenediamine Amines having a hydroxyl group can also be used. These chain extenders can be used alone or in combination of two or more.
A monovalent active hydrogen compound can also be used as a terminal blocking agent for terminating the reaction. Such compounds include, for example, dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, when it is desired to introduce a carboxyl group into the polyurethane resin, an amino acid such as glycine or L-alanine can be used as a reaction terminator. These terminal blocking agents can be used alone or in combination of two or more.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用するポリウレタン樹脂は、例えば、ポリプロピレングリコールおよび併用ポリオールとジイソシアネート化合物とをイソシアネート基が過剰となる割合で反応させ、末端イソシアネート基のプレポリマーを得、得られるプレポリマーを、適当な溶剤中、すなわち、ノントルエン系グラビアインキ用の溶剤として通常用いられる、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤；メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノールなどのアルコール系溶剤；メチルシクロヘキサン、エチルシクロヘキサンなどの炭化水素系溶剤；あるいはこれらの混合溶剤の中で、鎖伸長剤および（または）末端封鎖剤と反応させる二段法、あるいはポリプロピレングリコールおよび併用ポリオール、ジイソシアネート化合物、鎖伸長剤および（または）末端封鎖剤を上記のうち適切な溶剤中で一度に反応させる一段法により製造される。これらの方法のなかでも、均一なポリウレタン樹脂を得るには、二段法によることが好ましい。また、ポリウレタン樹脂を二段法で製造する場合、鎖伸長剤および（または）末端封鎖剤のアミノ基の合計（当量比）が１／０．９〜１．３の割合になるように反応させることが好ましい。イソシアネート基とアミノ基との当量比が１／１．３より小さいときは、鎖伸長剤および（または）末端封鎖剤が未反応のまま残存し、ポリウレタン樹脂が黄変したり、印刷後臭気が発生したりする場合がある。 The polyurethane resin used in the method for producing a laminate ink composition for ultraviolet shielding flexible packaging of the present invention is prepared, for example, by reacting a polypropylene glycol and a combined polyol with a diisocyanate compound at a ratio of an excess of isocyanate groups, and pre-treating the terminal isocyanate groups. A polymer is obtained, and the obtained prepolymer is dissolved in a suitable solvent, that is, an ester solvent such as ethyl acetate, propyl acetate, or butyl acetate which is usually used as a solvent for a non-toluene gravure ink; acetone, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol; hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane; or a mixed solvent thereof. , A two-stage method of reacting with a chain extender and / or an end capping agent, or reacting polypropylene glycol and a combined polyol, a diisocyanate compound, a chain extender and / or an end capping agent at once in an appropriate solvent among the above. It is manufactured by a one-stage method. Among these methods, the two-stage method is preferred for obtaining a uniform polyurethane resin. When the polyurethane resin is produced by a two-step method, the reaction is carried out so that the total (equivalent ratio) of the amino groups of the chain extender and / or the terminal blocking agent becomes 1 / 0.9 to 1.3. Is preferred. When the equivalent ratio of the isocyanate group to the amino group is less than 1 / 1.3, the chain extender and / or the terminal blocking agent remain unreacted, and the polyurethane resin yellows and odor after printing. May occur.
このようにして得られるポリウレタン樹脂の重量平均分子量は、１５，０００〜１００，０００の範囲内で且つラミネートインキ組成物のフィルム基材への密着性、耐スクラッチ性を得る点からガラス転移点（Ｔｇ）−４５〜−１０℃であることが好ましく、より好ましくは重量平均分子量２０，０００〜６０，０００の範囲である。ポリウレタン樹脂の重量平均分子量が１５，０００未満の場合には、得られるインキの組成物の耐ブロッキング性、印刷被膜の強度や耐油性などが低くなる傾向があり、１００，０００を超える場合には、得られるインキ組成物の粘度が高くなり、印刷被膜表面の平滑性が低下し、光沢が低くなる傾向がある。
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用するポリウレタン樹脂の含有量は、インキの被印刷体への接着性を十分にする観点から、最終的に溶剤類で調整されたラミネートインキ総質量に対して４質量％以上、適度なインキ粘度やインキ製造時・印刷時の作業効率の観点から２５質量％以下が好ましく、更には６〜１５質量％の範囲が好ましい。
The weight average molecular weight of the polyurethane resin thus obtained is in the range of 15,000 to 100,000, and the glass transition point (from the viewpoint of obtaining the adhesion of the laminated ink composition to the film substrate and the scratch resistance). Tg) -45 to -10 ° C, more preferably 20,000 to 60,000. When the weight average molecular weight of the polyurethane resin is less than 15,000, the blocking resistance of the obtained ink composition, the strength and oil resistance of the printed film tend to be low, and when it exceeds 100,000. In addition, the viscosity of the obtained ink composition tends to increase, the smoothness of the surface of the print film decreases, and the gloss tends to decrease.
The content of the polyurethane resin used in the method for producing the ultraviolet shielding soft packaging laminate ink composition of the present invention was finally adjusted with a solvent from the viewpoint of sufficient adhesion of the ink to a printing medium. The content is preferably 4% by mass or more based on the total mass of the lamination ink, and 25% by mass or less, and more preferably 6 to 15% by mass, from the viewpoints of appropriate ink viscosity and working efficiency during ink production and printing.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で用いるポリウレタン樹脂は、前述の組成であれば特に制限なく用いることができるが、これらの中でも、ウレタン樹脂中に活性水素含有官能基、例えば、水酸基、一級、又は二級のアミノ基等を含有しているものが、ウレタン樹脂とブロックイソシアネートの架橋が円滑に進行して、得られる印刷インキ層が強固になることから好ましい。なお、前記ウレタン樹脂中に活性水素含有官能基が含まれていなくても、インキ層を高温で加熱すれば、活性水素を含有したウレタン樹脂を用いた場合と同様な結果が得られる。 The polyurethane resin used in the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention can be used without any particular limitation as long as it has the above-mentioned composition. Among them, active hydrogen-containing functional groups in the urethane resin, For example, those containing a hydroxyl group, a primary or secondary amino group and the like are preferable because the crosslinking between the urethane resin and the blocked isocyanate proceeds smoothly and the obtained printing ink layer becomes strong. Even when the urethane resin does not contain an active hydrogen-containing functional group, if the ink layer is heated at a high temperature, the same result as in the case of using the active hydrogen-containing urethane resin can be obtained.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法では、水酸基を有する塩化ビニル酢酸ビニル共重合樹脂は、二種類の方法で得ることができる。一つは塩化ビニルモノマー、酢酸ビニルモノマーおよびビニルアルコールを適当な割合で共重合して得られる。もう一つは、塩化ビニルと酢酸ビニルを共重合した後、酢酸ビニルを一部ケン化することにより得られる。水酸基を有する塩化ビニル酢酸ビニル共重合樹脂は、塩化ビニル、酢酸ビニルおよびビニルアルコールのモノマー比率により樹脂被膜の性質や樹脂溶解挙動が決定される。即ち、塩化ビニルは樹脂被膜の強靭さや硬さを付与し、酢酸ビニルは接着性や柔軟性を付与し、ビニルアルコールは極性溶剤への良好な溶解性を付与する。 In the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention, a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group can be obtained by two types of methods. One is obtained by copolymerizing a vinyl chloride monomer, a vinyl acetate monomer and vinyl alcohol at an appropriate ratio. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying vinyl acetate. The properties of the resin film and the dissolution behavior of the vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group are determined by the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride gives the toughness and hardness of the resin film, vinyl acetate gives adhesion and flexibility, and vinyl alcohol gives good solubility in polar solvents.
本製造方法で作製した紫外線遮蔽軟包装用ラミネート用インキ組成物として使用する場合、接着性、耐ブロッキング性、耐スクラッチ性、印刷適性等全ての性能を満足する必要があるため、水酸基を有する塩化ビニル酢酸ビニル共重合樹脂は適正なモノマー比率が存在する。即ち、水酸基を有する塩化ビニル酢酸ビニル共重合樹脂１００質量部に対し、塩化ビニルは８０〜９５質量部が好ましい。８０質量部未満だと樹脂被膜の強靭さ劣り、耐ブロッキング性、耐スクラッチ性が低下する。９５質量部を超えると樹脂被膜が硬くなりすぎ、接着性が低下する。また、ビニルアルコールから得られる水酸基価は５０〜２００ｍｇＫＯＨ／ｇが好ましい。５０ｍｇＫＯＨ／ｇ未満だと極性溶媒への溶解性が劣り、印刷適性が不良となる。２００ｍｇＫＯＨ／ｇを超えると耐水性が低下する傾向にある。
本製造方法で使用する塩酢ビニル酢酸ビニル共重合樹脂の添加量は、仕上がったラミネート用インキ組成物の塗膜の強靭さ、耐ブロッキング性、耐スクラッチ性の観点からラミネート用インキ組成物全量の０．５〜１５質量％が好ましく、１〜１０質量％であればより好ましい。
When used as an ink composition for lamination for ultraviolet shielding flexible packaging produced by this production method, it is necessary to satisfy all performances such as adhesion, blocking resistance, scratch resistance, printability, etc. The vinyl-vinyl acetate copolymer resin has an appropriate monomer ratio. That is, the amount of vinyl chloride is preferably 80 to 95 parts by mass based on 100 parts by mass of the vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group. If the amount is less than 80 parts by mass, the toughness of the resin film is poor, and the blocking resistance and the scratch resistance are reduced. If it exceeds 95 parts by mass, the resin film becomes too hard, and the adhesiveness decreases. The hydroxyl value obtained from vinyl alcohol is preferably from 50 to 200 mgKOH / g. If it is less than 50 mgKOH / g, the solubility in polar solvents is poor, and the printability is poor. If it exceeds 200 mgKOH / g, the water resistance tends to decrease.
The addition amount of the vinyl chloride vinyl acetate / vinyl acetate copolymer resin used in the present production method is based on the total amount of the laminating ink composition from the viewpoint of the toughness of the coating film of the finished laminating ink composition, blocking resistance, and scratch resistance. It is preferably from 0.5 to 15% by mass, more preferably from 1 to 10% by mass.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法では、ハイドロゲンジメチコン処理した酸化亜鉛を必須とする。
本発明の製造方法で使用する酸化亜鉛としては、平均粒子径が５〜５０ｎｍ、好ましくは１５〜４０ｎｍのものを使用できる。酸化亜鉛をハイドロゲンジメチコン処理する場合、無処理の酸化亜鉛に対して直にハイドロゲンジメチコン処理したものと、粒子の不活性化を目的に酸化亜鉛粒子表面に高密度シリカ層をコーティングすることで、粒子表面を一旦高密度シリカ覆った上で、更にハイドロゲンジメチコン処理したものに大別できるが、本発明の製造方法で使用する酸化亜鉛としては、前者の無処理の酸化亜鉛に対して直にハイドロゲンジメチコン処理したものがより好ましい。その理由としては、後者の酸化亜鉛粒子表面を高密度シリカ層で覆い不活性化させ、酸化亜鉛の凝集力を弱める手法では、前記高密度シリカ層が含水性シリカであるため、本発明の製造方法によるインキ組成物の練肉工程で欲する疎水性を妨げ、混合する樹脂成分や溶剤との高分散性が低下する傾向にあることが挙げられる。
また、前記した無処理の酸化亜鉛に対して直にハイドロゲンジメチコン処理する場合、酸化亜鉛粒子表面を均一に且つ完全にシリコーンが覆い尽くし、粒子を粉砕しても活性面が露出しない湿式処理よりも、酸化亜鉛粒子表面の一部が露出し、活性面が露出した乾式処理をしたものの方が結果的にインキ組成物の分散性が向上しより好ましい。
In the process for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention, hydrogen dimethicone-treated zinc oxide is essential.
As the zinc oxide used in the production method of the present invention, those having an average particle diameter of 5 to 50 nm, preferably 15 to 40 nm can be used. When treating zinc oxide with hydrogen dimethicone, the untreated zinc oxide is treated directly with hydrogen dimethicone, and the zinc oxide particles are coated with a high-density silica layer on the surface to inactivate the particles. The surface is once covered with high-density silica, and can be roughly classified into those treated with hydrogen dimethicone. The zinc oxide used in the production method of the present invention is hydrogen dimethicone directly with respect to the former untreated zinc oxide. Treated ones are more preferred. The reason is that, in the latter method, the surface of the zinc oxide particles is covered with a high-density silica layer to inactivate and weaken the cohesive force of the zinc oxide. In the method, the ink composition tends to prevent the desired hydrophobicity of the ink composition in the meat-milling step, and the high dispersibility with the resin component and the solvent to be mixed tends to decrease.
In addition, when hydrogen dimethicone treatment is directly applied to the untreated zinc oxide, the surface of the zinc oxide particles is uniformly and completely covered with silicone, and the wet treatment in which the active surface is not exposed even when the particles are pulverized is performed. A dry treatment in which a part of the surface of the zinc oxide particles is exposed and the active surface is exposed is more preferable because the dispersibility of the ink composition is improved as a result.
本発明の製造方法で使用する酸化亜鉛に施すハイドロゲンジメチコン処理に用いられるシリコーンとしては、例えばメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロゲンポリシロキサン、メチルシクロポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、オクタメチルトリシロキサン、テトラデカメチルヘキサシロキサン、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン・メチル（ポリオキシプロピレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシプロピレン）シロキサン共重合体、ジメチルシロキサン・メチルセチルオキシシロキサン共重合体、ジメチルシロキサン・メチルステアロキシシロキサン共重合体等の各種シリコーン油を挙げることができる。中でも、メチルハイドロゲンポリシロキサンやメチルポリシロキサンが好ましい。
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用する酸化亜鉛は、最終的に溶剤類で調整されたラミネートインキ総質量に対して５〜３０質量％が好ましく、うち無処理の酸化亜鉛に直にハイドロゲンジメチコン処理した酸化亜鉛の添加量は、酸化亜鉛全量の１〜１０質量％であり、好ましくは２〜７質量％であり、より好ましくは３〜５質量％である。
Examples of the silicone used in the hydrogen dimethicone treatment applied to the zinc oxide used in the production method of the present invention include, for example, methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethyl Cyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxy Ethylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methylcetyl Carboxymethyl copolymer, it may be mentioned various silicone oils such as dimethyl siloxane-methyl stearoxysiloxane copolymer. Among them, methyl hydrogen polysiloxane and methyl polysiloxane are preferable.
The zinc oxide used in the method for producing a laminate ink composition for ultraviolet shielding flexible packaging according to the present invention is preferably 5 to 30% by mass based on the total mass of the laminate ink finally adjusted with solvents. The amount of zinc oxide that has been directly subjected to hydrogen dimethicone treatment to zinc oxide is 1 to 10% by mass, preferably 2 to 7% by mass, and more preferably 3 to 5% by mass of the total amount of zinc oxide.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法で使用する有機溶剤は、芳香族有機溶剤を除く有機溶剤を使用することができる。例えばアセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ｎ−プロピル、酢酸ブチル、酢酸アミル、ギ酸エチル、プロピオン酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤、メタノール、エタノール、イソプロピルアルコール、ｎ−プロパノール、イノプロパノール、ｎ−ブタノール、プロピレングリコールモノメチルエーテル等のアルコール系溶剤、エチレングリコール（モノ，ジ）メチルエーテル、エチレングリコール（モノ，ジ）エチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノイソプロピルエーテル、モノブチルエーテル、ジエチレングリコール（モノ，ジ）メチルエーテル、ジエチレングリコール（モノ，ジ）エチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール（モノ，ジ）メチルエーテル、プロピレングリコール（モノ，ジ）メチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール（モノ，ジ）メチルエーテル等のグリコールエーテル系があげられ、これらを単独または２種以上の混合物で用いることができる。近年、作業環境の観点から、トルエン、キシレン、ソルベッソ＃１００、ソルベッソ＃１５０といった芳香族系溶剤を用いないことが望ましい。中でもポリウレタン樹脂への溶解性の観点から、酢酸エチル、イソプロピルアルコール、ノルマルプロピルアセテート、メチルエチルケトンの混合液がより好ましい。 As the organic solvent used in the method for producing a laminate ink composition for ultraviolet shielding flexible packaging of the present invention, an organic solvent other than an aromatic organic solvent can be used. For example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, and propylene glycol monomethyl ether acetate; Solvents, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-propanol, inopropanol, n-butanol, and propylene glycol monomethyl ether; ethylene glycol (mono, di) methyl ether; ethylene glycol (mono, di) ethyl ether; Ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol Tylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether And glycol ethers such as dipropylene glycol (mono, di) methyl ether. These can be used alone or in a mixture of two or more. In recent years, from the viewpoint of the working environment, it is desirable not to use an aromatic solvent such as toluene, xylene, Solvesso # 100 and Solvesso # 150. Among them, a mixed solution of ethyl acetate, isopropyl alcohol, normal propyl acetate, and methyl ethyl ketone is more preferable from the viewpoint of solubility in the polyurethane resin.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法では、高煎断力を与えることで練肉、分散した後小片化させることを特徴とする。一般的に軟包装用ラミネートインキでは、小煎断力のビーズミル分散機を使用するが一般的であるが、本発明では高煎断力による分散を必須とし、具体的には練肉時に高い煎断力が得られる２本ロールミルが最も好ましい。２本ロールミルの練肉装置としては、例えばロールは金属（鋼鉄）製であり、ロール外径５０ｃｍ〜２ｍ、ロールの重量０．５〜７トン、ロール間が０．３〜３０ｍｍ、ロールの回転数が３０〜３００回転／分、ロール温度５０〜９５℃にて、３０〜３６０分連続連肉できれば良い。練肉が進行するに従い溶剤分が揮発し、練肉完了後常温（２５℃）に冷却した段階で固化し、最終的にはチップ状の小片の顔料樹脂固形物となり、この固形物を再度、樹脂、溶剤類に溶かし紫外線遮蔽軟包装用ラミネートインキを作製する。 The method for producing a laminated ink composition for ultraviolet shielding soft packaging according to the present invention is characterized in that a high decoction force is applied to cut and disperse the meat into pieces. In general, a laminating ink for soft packaging uses a bead mill dispersing machine with a small roasting force, but in the present invention, dispersion by a high roasting force is essential. Most preferred is a two-roll mill that can provide shear. For example, the roll is made of metal (steel), the outer diameter of the roll is 50 cm to 2 m, the weight of the roll is 0.5 to 7 tons, the gap between the rolls is 0.3 to 30 mm, and the rotation of the roll is as a two-roll mill. It suffices if the continuous meat can be continuously produced at a number of 30 to 300 revolutions / minute and a roll temperature of 50 to 95 ° C. for 30 to 360 minutes. As the meat proceeds, the solvent evaporates and solidifies at the stage of cooling to room temperature (25 ° C.) after the completion of the meat, and finally becomes a pigment-resin solid in the form of chip-like pieces. Dissolve in resins and solvents to produce laminating ink for ultraviolet shielding soft packaging.
本発明の製造方法では更に必要に応じて、顔料分散剤、レベリング剤、消泡剤、ワックス、可塑剤、芳香剤、難燃剤なども含むこともできる。 In the production method of the present invention, a pigment dispersant, a leveling agent, a defoaming agent, a wax, a plasticizer, a fragrance, a flame retardant, and the like can be further contained as necessary.
本発明を実施例によりさらに具体的に説明する。以下、「部」及び「％」は、いずれも質量基準によるものとする。
なお、本発明におけるＧＰＣ（ゲルパーミエーションクロマトグラフィー）による数平均分子量（ポリスチレン換算）の測定は東ソー(株)社製ＨＬＣ８２２０システムを用い以下の条件で行った。
分離カラム：東ソー（株）製ＴＳＫｇｅｌＧＭＨＨＲ−Ｎを４本使用。カラム温度：４０℃。移動層：和光純薬工業（株）製テトラヒドロフラン。流速：１．０ｍｌ／分。試料濃度：１.０質量％。試料注入量：１００マイクロリットル。検出器：示差屈折計。
また、ガラス転移温度（Ｔｇ）の測定は、示差雰囲気下、冷却装置を用い温度範囲−８０〜４５０℃、昇温温度１０℃／分の条件で走査を実施した。
The present invention will be described more specifically with reference to examples. Hereinafter, “parts” and “%” are both based on mass.
The measurement of the number average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) in the present invention was performed under the following conditions using an HLC8220 system manufactured by Tosoh Corporation.
Separation column: 4 TSKgelGMHHR-N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliter. Detector: Differential refractometer.
Further, the measurement of the glass transition temperature (Tg) was carried out in a differential atmosphere using a cooling device under the conditions of a temperature range of -80 to 450 ° C and a heating temperature of 10 ° C / min.
調整例１〜６に従い、本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法によるベースインキＡ〜Ｆを調製した。
ベースインキＡ〜Ｆの配合比率は次の通りである。
ベースインキＥについては、ハイドロゲンジメチコン処理してない酸化亜鉛を使用した。
ベースインキＧについては、分散剤を削除した。
ポリウレタン樹脂 ３３．０部
水酸基を有する塩酢ビニル酢酸ビニル共重合樹脂 ３．０部
各種酸化亜鉛 ６０．０部
分散剤 ４．０部
合 計 １００．０部
According to Preparation Examples 1 to 6, base inks A to F were prepared by the method for producing a laminated ink composition for ultraviolet shielding flexible packaging of the present invention.
The mixing ratio of the base inks A to F is as follows.
As the base ink E, zinc oxide not subjected to hydrogen dimethicone treatment was used.
For base ink G, the dispersant was omitted.
Polyurethane resin 33.0 parts Vinyl chloride acetate vinyl acetate copolymer resin having hydroxyl group 3.0 parts Various zinc oxide 60.0 parts
4.0 parts of dispersant
Total 100.0 copies
〔調整例１：ベースインキＡの作製〕
日立化成（株）製ポリウレタン樹脂ＴＡ２４−５４２Ｄ（Ｔｇ：−２８℃、Ｍｗ：３９，０００）を３３部、日信化学工業(株)製 塩酢ビニル酢酸ビニル共重合樹脂ソルバインＡを３部、堺化学工業(株)製ＦＩＮＥＸ−５０Ｓ−ＬＰ２（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の４重量％含む）を６０部、ルーブリゾール社製ε−カプロラクトン系高分子分散剤ソルスパース２４０００を４部混合した後、これを２本鋼鉄ロール練肉機に次の条件下で１２０分間連続練肉した後、２５℃に冷却するまで放置し、固化したベースインキを練肉機から回収し、チップ状に小片化させたベースインキＡを作製した。鋼鉄ロール径１ｍ、ロール重量３トン、ロールのニップ間：２ｍｍ、回転数２００ｒｐｍ、ロール温度：８０℃
[Adjustment Example 1: Production of Base Ink A]
33 parts of a polyurethane resin TA24-542D (Tg: -28 ° C, Mw: 39,000) manufactured by Hitachi Chemical Co., Ltd., 3 parts of a vinyl acetate vinyl acetate copolymer resin Solvain A manufactured by Nissin Chemical Industry Co., Ltd. 60 parts of FINEX-50S-LP2 manufactured by Sakai Chemical Industry Co., Ltd. (containing untreated zinc oxide (average particle diameter: 20 nm) and hydrogen dimethicone-treated zinc oxide at 4% by weight of the total amount of zinc oxide), ε manufactured by Lubrizol Corporation After mixing 4 parts of caprolactone-based polymer dispersing agent Solsperse 24000, the mixture was continuously milled in a two-roll steel mill under the following conditions for 120 minutes, then left to cool to 25 ° C. and solidified. The base ink was collected from a meat mill, and a base ink A was obtained which was chipped into small pieces. Steel roll diameter 1m, roll weight 3 ton, nip between rolls: 2mm, rotation speed 200rpm, roll temperature: 80 ° C
〔調整例２：ベースインキＢの作製〕
ベースインキＡの日立化成（株）製ポリウレタン樹脂ＴＡ２４−５４２Ｄ代わりに、三洋化成（株）製ポリウレタン樹脂ＩＢ−５０１（Ｔｇ：−２６℃、Ｍｗ：２５，０００）を同量３３部添加する他は、全て同じ配合、同じ手順にてベースインキＢを作製した。
[Adjustment Example 2: Preparation of base ink B]
33 parts of polyurethane resin IB-501 (Tg: -26 ° C, Mw: 25,000) manufactured by Sanyo Chemical Co., Ltd. are added instead of polyurethane resin TA24-542D manufactured by Hitachi Chemical Co., Ltd. of base ink A. Prepared a base ink B in the same formulation and in the same procedure.
〔調整例３：ベースインキＣの作製〕
ベースインキＡの堺化学工業(株)製ＦＩＮＥＸ−５０Ｓ−ＬＰ２の代わりに、同社製
ＦＩＮＥＸ−５０−ＬＰＴ（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の７重量％含む）を同量６０部添加する他は、全て同じ配合、同じ手順にてベースインキＣを作製した。
[Adjustment Example 3: Production of base ink C]
Instead of the base ink A, FINEX-50S-LP2 manufactured by Sakai Chemical Industry Co., Ltd., FINEX-50-LPT (manufactured by the company, untreated zinc oxide (average particle diameter: 20 nm), treated with hydrogen dimethicone by hydrogen dimethicone, and the total amount of zinc oxide) Was added in the same amount and in the same procedure, except that the same amount of 60 parts was added.
〔調整例４：ベースインキＤの作製〕
ベースインキＡの堺化学工業(株)製ＦＩＮＥＸ−５０Ｓ−ＬＰ２の代わりに、同社製
ＦＩＮＥＸ−５０Ｗ−ＬＰ２（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の４重量％と、高密度シリカ層をコーティングした酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の２１重量％含む）を同量６０部添加する他は、全て同じ配合、同じ手順にてベースインキＤを作製した。
[Adjustment Example 4: Production of base ink D]
In place of FINEX-50S-LP2 manufactured by Sakai Chemical Industry Co., Ltd. of base ink A, total amount of zinc oxide obtained by treating FINEX-50W-LP2 (untreated zinc oxide (average particle diameter: 20 nm) with hydrogen dimethicone and hydrogen dimethicone) was used. And 4 parts by weight of zinc oxide coated with a high-density silica layer (average particle diameter: 20 nm) containing 60 parts of the same amount of zinc oxide treated with hydrogen dimethicone (including 21% by weight of the total amount of zinc oxide). A base ink D was prepared by the same procedure as in the blending.
〔調整例５：ベースインキＥの作製〕
ベースインキＡの堺化学工業(株)製ＦＩＮＥＸ−５０Ｓ−ＬＰ２の代わりに、同社製
ＦＩＮＥＸ−Ｈ５０（無処理の酸化亜鉛（平均粒子径２０ｎｍ）に高密度シリカ層をコーティング、ハイドロゲンジメチコン処理共にされていない酸化亜鉛）を同量６０部添加する他は、全て同じ配合、同じ手順にてベースインキＥを作製した。
[Adjustment Example 5: Preparation of base ink E]
Instead of base ink A, FINEX-50S-LP2 manufactured by Sakai Chemical Industry Co., Ltd., FINEX-H50 (untreated zinc oxide (average particle diameter: 20 nm)) is coated with a high-density silica layer and treated with hydrogen dimethicone. A base ink E was prepared in the same composition and in the same procedure, except that the same amount of zinc oxide (60 parts) was added.
〔調整例６：ベースインキＦの作製〕
ベースインキＡからの塩酢ビニル酢酸ビニル共重合樹脂ソルバインＡ ３部を削除し、日立化成（株）製ポリウレタン樹脂ＴＡ２４−５４２Ｄを３３部、堺化学工業(株)製ＦＩＮＥＸ−５０Ｓ−ＬＰ２（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の４質量％含む）を６０部、ルーブリゾール社製ε−カプロラクトン系高分子分散剤ソルスパース２４０００を４部混合した他は、全て同じ手順にてベースインキＦを作製した。
[Adjustment Example 6: Preparation of base ink F]
3 parts of vinyl acetate / vinyl acetate copolymer resin Solvain A from base ink A were deleted, 33 parts of polyurethane resin TA24-542D manufactured by Hitachi Chemical Co., Ltd., FINEX-50S-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.) To the treated zinc oxide (average particle diameter: 20 nm), hydrogen dimethicone-treated zinc oxide (containing 4% by mass of the total amount of zinc oxide) was mixed with 60 parts, and Lubrizol ε-caprolactone polymer dispersant Solsperse 24000 (4 parts) was mixed. Otherwise, base ink F was prepared in the same procedure.
〔調整例７：ベースインキＧの作製〕
ベースインキＡからルーブリゾール社製ε−カプロラクトン系高分子分散剤ソルスパース２４０００の４部を削除した他は、全て同じ手順にてベースインキＧを作製した。
[Adjustment Example 7: Preparation of base ink G]
Base ink G was prepared in the same procedure except that 4 parts of Sol-Sperse 24000, an ε-caprolactone polymer dispersant manufactured by Lubrizol Co., were removed from Base Ink A.
上記、ベースインキＡ〜Ｆで使用する酸化亜鉛を列記すると次の通りである。
表１には、各酸化亜鉛の構成を質量比率（％）で示す。平均粒子径は全て２０ｎｍである。
・ベースインキＡ、Ｂ
：ａ）ＦＩＮＥＸ−５０Ｓ−ＬＰ２（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の４質量％含む）
・べースインキＣ
：ｂ）ＦＩＮＥＸ−５０−ＬＰＴ（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の７質量％含む）
・ベースインキＤ
：ｃ）ＦＩＮＥＸ−５０Ｗ−ＬＰ２（無処理の酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の４質量％と、高密度シリカ層をコーティングした酸化亜鉛（平均粒子径２０ｎｍ）にハイドロゲンジメチコン処理した酸化亜鉛を酸化亜鉛全量の２１質量％含む）
・ベースインキＥ
：ｄ）ＦＩＮＥＸ−Ｈ５０（無処理の酸化亜鉛（平均粒子径２０ｎｍ）に高密度シリカ層をコーティング、ハイドロゲンジメチコン処理共にされていない酸化亜鉛）
The zinc oxides used in the base inks A to F are listed below.
Table 1 shows the composition of each zinc oxide by mass ratio (%). The average particle diameters are all 20 nm.
・ Base inks A and B
: A) FINEX-50S-LP2 (containing untreated zinc oxide (average particle diameter: 20 nm) and hydrogen dimethicone-treated zinc oxide in an amount of 4% by mass of the total amount of zinc oxide)
・ Base ink C
: B) FINEX-50-LPT (containing untreated zinc oxide (average particle diameter: 20 nm) and hydrogen dimethicone-treated zinc oxide at 7% by mass of the total amount of zinc oxide)
・ Base ink D
: C) FINEX-50W-LP2 (untreated zinc oxide (average particle size: 20 nm), hydrogen dimethicone-treated zinc oxide, 4% by mass of the total amount of zinc oxide, and zinc oxide coated with a high-density silica layer (average particle size) 20 nm) containing 21% by mass of zinc oxide treated with hydrogen dimethicone)
・ Base ink E
: D) FINEX-H50 (untreated zinc oxide (average particle diameter 20 nm) coated with a high-density silica layer, not treated with hydrogen dimethicone)
調整例８〜１４に従い、従来からの分散方法であるビーズミルによるベースインキＨ〜Ｎについて、ジルコニアビーズミルを用いて調製した。尚、ジルコニアビーズミルによる練肉では必ず溶剤分の添加が必要である事から、ベースインキを希釈して最終的に紫外線遮蔽軟包装用ラミネートインキとする際に使用する溶剤である、ノルマルプロピルアセテート及びイソプロピルアルコールを各々４部ずつ、練肉に最小限の必要な量を添加し練肉調製した。 In accordance with Preparation Examples 8 to 14, base inks H to N using a bead mill, which is a conventional dispersion method, were prepared using a zirconia bead mill. In addition, since the addition of the solvent component is always necessary in the crushed meat by the zirconia bead mill, the solvent used when diluting the base ink and finally forming the ultraviolet shielding soft packaging laminating ink, normal propyl acetate and A minimum required amount of isopropyl alcohol was added to each of 4 parts of the ground meat to prepare a ground meat.
〔調整例８：ベースインキＨの作製〕
ベースインキＡと同様の構成に、更にノルマルプロピルアセテート４部、イソプロピルアルコール４部を混合した後、直径５ｍｍのジルコニアビーズを２００ｇ入れ、ペイントコンディショナーにて６０分間練肉し、ベースインキＨを作製した。
[Adjustment Example 8: Preparation of base ink H]
After further mixing 4 parts of normal propyl acetate and 4 parts of isopropyl alcohol with the same composition as the base ink A, 200 g of zirconia beads having a diameter of 5 mm was added, and the mixture was kneaded with a paint conditioner for 60 minutes to prepare a base ink H. .
〔調整例９〜１４：ベースインキＩ〜Ｎの作製〕
ベースインキＢ〜Ｇの配合各々に対して、ベースインキＨと同様にノルマルプロピルアセテート４部、イソプロピルアルコール４部を混合した後、ベースインキＨと同様に直径５ｍｍのジルコニアビーズを２００ｇ入れ、ペイントコンディショナーにて６０分間練肉し、ベースインキＩ〜Ｎを作製した。
[Adjustment Examples 9 to 14: Preparation of base inks I to N]
After mixing 4 parts of normal propyl acetate and 4 parts of isopropyl alcohol with each of the base inks B to G as in the case of the base ink H, 200 g of zirconia beads having a diameter of 5 mm was put in the same manner as in the base ink H, and the paint conditioner was added. For 60 minutes to prepare base inks I to N.
高煎断性練肉（２本ロール）によるベースインキＡ〜Ｇの配合を表２に、ジルコニアビーズミ練肉によるベースＨ〜Ｎの配合を表３に示す。 Table 2 shows the composition of the base inks A to G by the high roasting paste (two rolls), and Table 3 shows the composition of the bases H to N by the zirconia bead paste.
［実施例１］
ベースインキＡを３３．３部、ウレタン樹脂ＩＢ−９１５（三洋化成（株）社製）を７部、ロジンニスＲ６２４−５０１（江南化成（株）社製）を１部、添加剤スーパークロン３４１Ｅトルエン（塩素化ポリプロピレン系、日本製紙（株）社製）を１．６部、酢酸エチル７部、ノルマルプロピルアセテート１４部、イソプロピルアルコール１４部、消泡剤ＳＮ−３５３を０．１部加え練肉し、紫外線遮蔽軟包装用ラミネートインキを作製した。
仕上がったラミネートインキ全量中の酸化亜鉛は２０質量％を含有する。
得られたラミネートインキの粘度をメチルエチルケトン、酢酸エチル及びイソプロピルアルコールの混合溶液（重量比４０：４０：２０）で希釈し、ザーンカップ＃３（離合社製）で１６秒（２５℃）に調整し、版深３５μｍグラビア版を備えたグラビア校正機により
２軸延伸ポリプロピレンＯＰＰフィルム（東洋紡社製 Ｐ２１６１、厚み２０μｍ）とＰＥＴフィルム（東洋紡社製 Ｅ５１００、 厚み１２μ）のフィルム２種にベタ刷り印刷して４５℃で乾燥し、印刷物を得た。
[Example 1]
33.3 parts of base ink A, 7 parts of urethane resin IB-915 (manufactured by Sanyo Chemical Co., Ltd.), 1 part of rosin varnish R624-501 (manufactured by Gangnam Chemical Co., Ltd.), additive Supercron 341E toluene 1.6 parts of chlorinated polypropylene (manufactured by Nippon Paper Industries Co., Ltd.), 7 parts of ethyl acetate, 14 parts of normal propyl acetate, 14 parts of isopropyl alcohol, and 0.1 part of antifoaming agent SN-353 and kneaded meat. Then, an ultraviolet shielding soft packaging laminate ink was prepared.
Zinc oxide in the total amount of the finished lamination ink contains 20% by mass.
The viscosity of the obtained laminate ink was diluted with a mixed solution of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio: 40:40:20), and adjusted to 16 seconds (25 ° C.) with Zahn Cup # 3 (manufactured by Rigo Co., Ltd.). Using a gravure proofing machine equipped with a 35 μm gravure plate, two types of films, a biaxially stretched polypropylene OPP film (P2161 manufactured by Toyobo Co., thickness 20 μm) and a PET film (E5100 manufactured by Toyobo Co., thickness 12 μm), were printed by solid printing. It was dried at 45 ° C. to obtain a printed matter.
［実施例２〜５、及び比較例１〜９］
実施例２〜５についてベースインキＡ〜Ｄ、及びＧ、比較例１、２についてベースインＥ、Ｆを用いて、実施例１と同様の配合にてラミネートインキを作成し、同じ作製手順にて印刷物を作製した。尚、ジルコニアビーズミ練肉による比較例３〜９については、最終的に作製した紫外線遮蔽軟包装用ラミネートインキ全量中の酸化亜鉛の量を実施例１と同様２０質量％とすべく、例えば比較例３については、ベースインキＨを３６．６部、ウレタン樹脂ＩＢ−９１５（三洋化成（株）社製）を７部、ロジンニスＲ６２４−５０１（江南化成（株）社製）を１部、添加剤スーパークロン３４１Ｅトルエン（塩素化ポリプロピレン系、日本製紙（株）社製）を１．６部、酢酸エチル７部とした他、溶剤総量を合せるべくノルマルプロピルアセテート１０部、イソプロピルアルコール１０部、消泡剤ＳＮ−３５３を０．１部加えジルコニアビーズミにて練肉し、紫外線遮蔽軟包装用ラミネートインキを作製した。得られたラミネートインキの粘度を実施例１と同様にメチルエチルケトン、酢酸エチル及びイソプロピルアルコールの混合溶液（質量比４０：４０：２０）で希釈し、ザーンカップ＃３（離合社製）で１６秒（２５℃）に調整し、版深３５μｍグラビア版を備えたグラビア校正機により実施例１と同様にフィルム２種に印刷して４５℃で乾燥し、印刷物を得た。比較例３と同様の要領にて、比較例４〜９についてラミネートインキを作製し同様の手順にて印刷物を得た。
[Examples 2 to 5, and Comparative Examples 1 to 9]
Using the base inks A to D and G for Examples 2 to 5 and the base ins E and F for Comparative Examples 1 and 2, a laminate ink was prepared in the same formulation as in Example 1, and the same preparation procedure was used. Printed matter was produced. For Comparative Examples 3 to 9 using zirconia beads, the amount of zinc oxide in the total amount of the finally prepared lamination ink for ultraviolet shielding soft packaging was set to 20% by mass in the same manner as in Example 1, for example. For Example 3, 36.6 parts of base ink H, 7 parts of urethane resin IB-915 (manufactured by Sanyo Chemical Co., Ltd.), and 1 part of rosin varnish R624-501 (manufactured by Konan Kasei Co., Ltd.) were added. In addition to 1.6 parts of Supercron 341E toluene (chlorinated polypropylene, manufactured by Nippon Paper Industries Co., Ltd.) and 7 parts of ethyl acetate, 10 parts of normal propyl acetate, 10 parts of isopropyl alcohol, 0.1 part of foaming agent SN-353 was added, and the mixture was kneaded with zirconia beads to prepare a laminate ink for ultraviolet shielding soft packaging. The viscosity of the obtained laminating ink was diluted with a mixed solution of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (mass ratio 40:40:20) in the same manner as in Example 1, and the mixture was diluted with Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 16 seconds ( (25 ° C.), printing was performed on two kinds of films in the same manner as in Example 1 using a gravure proofer equipped with a gravure plate having a depth of 35 μm, and dried at 45 ° C. to obtain a printed material. In the same manner as in Comparative Example 3, a laminate ink was prepared for Comparative Examples 4 to 9, and a printed matter was obtained in the same procedure.
得られた印刷物について、ポリプロピレンＯＰＰフィルム、及びＰＥＴフィルム各々への密着性、スクラッチ性、透明度、紫外線透過率について評価した。また、最終的に仕上がった紫外線遮蔽軟包装用ラミネートインキの酸化亜鉛の粒度分布について、粒度分布測定装置によるレーザー解析により調査した。その結果を表４、５に示す。尚、評価は下記の試験方法にて行った。 The resulting printed matter was evaluated for adhesion to each of a polypropylene OPP film and a PET film, scratchability, transparency, and ultraviolet transmittance. In addition, the particle size distribution of zinc oxide in the finally finished ultraviolet shielding soft packaging laminate ink was investigated by laser analysis using a particle size distribution measuring device. Tables 4 and 5 show the results. In addition, evaluation was performed by the following test methods.
１）密着性
紫外線遮蔽軟包装用ラミネートインキをベタ刷りしたポリプロピレンＯＰＰフィルム、及びＰＥＴフィルム各々を１００℃にて１０秒間オーブン加熱した後、常温（２５℃）で１日放置後、印刷面にセロハンテープ（ニチバン製）を貼り付け、これを急速に剥がしたときのレジスト印刷皮膜の外観の状態を目視判定した。なお判定基準は次の５段階とした。
５：印刷皮膜が全く剥がれなかった。
４：印刷皮膜の７０％以上〜９０％がフィルムに残った。
３：印刷皮膜の５０％以上〜７０％未満がフィルムに残った。
２：印刷皮膜の３０％以上〜５０％未満がフィルムに残った。
１：印刷皮膜の３０％以下がフィルムに残った。
1) Adhesiveness Each of the polypropylene OPP film and the PET film solid-printed with the laminating ink for ultraviolet shielding soft packaging is oven-heated at 100 ° C. for 10 seconds, then left at room temperature (25 ° C.) for one day, and then the cellophane is printed on the printed surface. A tape (manufactured by Nichiban) was affixed, and the appearance of the resist print film when the tape was rapidly removed was visually judged. The criteria were the following five steps.
5: The printed film was not peeled at all.
4: 70% or more to 90% of the print film remained on the film.
3: 50% or more to less than 70% of the printed film remained on the film.
2: 30% or more to less than 50% of the printed film remained on the film.
1: 30% or less of the print film remained on the film.
２）耐スクラッチ性
爪によりＯＰＰフィルム、及びＰＥＴフィルム各々の印刷皮膜を擦った際の外観の状態を目視判定した。なお判定基準は次の５段階とした。
５：１０回以上擦っても皮膜が剥がれない
４：１０回の擦れでわずかに皮膜が剥がれる
３：４〜５回の擦れで皮膜が剥がれる
２：２〜３回の擦れで皮膜が剥がれる
１：１回の擦れで皮膜が容易に剥がれる
2) Scratch resistance The appearance of the printed film of each of the OPP film and the PET film when the printed film was rubbed with a nail was visually judged. The criteria were the following five steps.
5: The film does not peel off even after rubbing 10 times or more. 4: The film peels off slightly after 10 rubs. 3: The film peels off after 4 to 5 rubs. 2: The film peels off after 2 to 3 rubs. The film easily peels off with one rub
３）透明度（ヘイズ）
日本電色社製（ＮＤＨ５０００）濁度計を用い、ＯＰＰフィルム及びＰＥＴフィルム各々の印刷部の透明度を計測した。数値が小さい程、透明度が高い。尚、印刷していない因みに、２軸延伸ポリプロピレンＯＰＰフィルム（東洋紡社製、厚み２０μｍ）の透明度は２．８であった。また、ＰＥＴフィルム（東洋紡社製 厚み１２μ）の透明度は２．６であった。
3) Transparency (haze)
Using a turbidity meter (NDH5000) manufactured by Nippon Denshoku Co., Ltd., the transparency of each printed portion of the OPP film and the PET film was measured. The smaller the value, the higher the transparency. Incidentally, the transparency of the biaxially stretched polypropylene OPP film (manufactured by Toyobo Co., Ltd., thickness: 20 μm) was 2.8 due to no printing. The transparency of the PET film (Toyobo Co., Ltd., thickness 12 μm) was 2.6.
４）紫外線透過率（％）
日本分光社製ＵＶ／ＶＩＳ ＳＰＥＣＴＲＯＭＥＴＥＲ（Ｖ−５７０ＤＳ）を用い、ＯＰＰ及びＰＥＴフィルム印刷部の紫外線透過率を測定した。 紫外線透過率は３６０ｎｍのところの透過率（％）を表記し、数値が小さい程、紫外線を遮断しており、数値が大きい程、紫外線が透過している。
4) UV transmittance (%)
The UV transmittance of the OPP and PET film printing portions was measured using UV / VIS SPECTROMETER (V-570DS) manufactured by JASCO Corporation. The ultraviolet transmittance indicates the transmittance (%) at 360 nm. The smaller the numerical value, the more the ultraviolet light is blocked, and the larger the numerical value, the more the ultraviolet light is transmitted.
５）粒度分布
日機装（株）社製マイクロトラック（Ｍｉｃｒｏｔｒａｃ）粒度分布測定装置ＭＴ３３００ＥＸＩＩによるレーザー解析により、最終的に仕上がった紫外線遮蔽軟包装用ラミネートインキの酸化亜鉛の粒度分布について調査した所、下記１，２の区分に分布状況が大別された。
１：酸化亜鉛全量の９５質量％が０．５ｎｍ以上１．１５ｎｍ未満に分布し、
分布の極大値を０．９５〜１．０５ｎｍの範囲に有する。
２：酸化亜鉛全量の９５質量％が１．１５ｎｍ以上１４ｎｍ未満に分布する。
5) Particle size distribution The particle size distribution of zinc oxide in the finally finished ultraviolet shielding soft packaging laminating ink was examined by laser analysis using a Microtrac particle size distribution analyzer MT3300EXII manufactured by Nikkiso Co., Ltd. The distribution situation was roughly divided into two categories.
1: 95% by mass of the total amount of zinc oxide is distributed in a range from 0.5 nm to less than 1.15 nm,
The distribution has a maximum value in the range of 0.95 to 1.05 nm.
2: 95% by mass of the total amount of zinc oxide is distributed at 1.15 nm or more and less than 14 nm.
実施例の製造方法では、密着性・耐スクラッチ性、紫外線に対しては高い遮断性を保持しつつ、可視光に対してはより高い透明性を再現できる。 In the manufacturing method of the embodiment, it is possible to reproduce higher transparency with respect to visible light while maintaining high adhesion / scratch resistance and high blocking property against ultraviolet rays.
本発明の紫外線遮蔽軟包装用ラミネートインキ組成物の製造方法では、可視光に対しては高い透明性を持ち、尚且つ紫外線に対しては高い遮断性を併せて発現し、食品、医薬品、コスメ、電子部品等のフィルム包材用途向けに幅広く展開し得る。 In the method for producing a laminated ink composition for ultraviolet shielding flexible packaging according to the present invention, the composition has high transparency to visible light and high shielding property to ultraviolet rays, and is used for foods, pharmaceuticals, cosmetics, and the like. It can be widely used for film packaging materials such as electronic parts.
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