JP4983581B2 - Laminate for laser marking - Google Patents
Laminate for laser marking Download PDFInfo
- Publication number
- JP4983581B2 JP4983581B2 JP2007319055A JP2007319055A JP4983581B2 JP 4983581 B2 JP4983581 B2 JP 4983581B2 JP 2007319055 A JP2007319055 A JP 2007319055A JP 2007319055 A JP2007319055 A JP 2007319055A JP 4983581 B2 JP4983581 B2 JP 4983581B2
- Authority
- JP
- Japan
- Prior art keywords
- laser
- laminate
- laser marking
- printing
- marking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 238000010330 laser marking Methods 0.000 title claims description 42
- 238000007639 printing Methods 0.000 claims description 90
- 239000011347 resin Substances 0.000 claims description 64
- 229920005989 resin Polymers 0.000 claims description 64
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- 238000000034 method Methods 0.000 claims description 23
- 229920003023 plastic Polymers 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 16
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 10
- 229920006255 plastic film Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910009372 YVO4 Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000012463 white pigment Substances 0.000 claims description 6
- 239000001052 yellow pigment Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical group [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
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- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
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- 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
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 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
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- BUJJNPWRTNNUCG-UHFFFAOYSA-L iron(2+);dibenzoate Chemical compound [Fe+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BUJJNPWRTNNUCG-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 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
- 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
- 238000010030 laminating Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- HGVIAKXYAZRSEG-UHFFFAOYSA-N n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1C HGVIAKXYAZRSEG-UHFFFAOYSA-N 0.000 description 1
- TVZIWRMELPWPPR-UHFFFAOYSA-N n-(2-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C TVZIWRMELPWPPR-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は、レーザ照射により、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層に目的とする文字、図形、コード等のマーキングを施すレーザマーキング用積層体に関する。 The present invention relates to a laser marking laminate in which marking of characters, figures, codes and the like is performed on an ink film layer formed from a printing ink containing a vinyl acetate resin by laser irradiation.
PL法(製造物責任法)が施行され、包装体、ラベル等には多種の印字が必要になっている。また、セキュリティー、あるいはトレーサビリティの観点からも印字および図柄等による表示の重要性が高まっている。
その表示には、医薬品、電子機器、電子部品、日用品、包装品等、及び多種多様な製品が関係している。実際の表示は、その製品の生産場所、流通経路、製品の特徴等を固有の文字、図形、コード等により表現し、製品自体に表示を組み込んだり、ラベル、シールにより情報を貼付することで行なわれている。
The PL Act (Product Liability Act) has been enforced, and various types of printing are required for packaging, labels, and the like. In addition, from the viewpoint of security or traceability, the importance of display by printing and design is increasing.
The display involves a wide variety of products such as pharmaceuticals, electronic devices, electronic components, daily necessities, and packaging products. The actual display is performed by expressing the production location, distribution channel, product characteristics, etc. of the product with unique characters, figures, codes, etc., and incorporating the display into the product itself, or pasting information with labels or stickers. It is.
従来、包装資材、ラベル、キャップ、フィルム、容器等への文字、図形の表示は、グラビア印刷法、フレキソ印刷法、オフセット印刷法、シルクスクリーン印刷法などの有版方式で行われてきた。また、スタンプ印刷法、インクジェット印刷法、感熱転写リボン法、刻印印刷法等でも行われている。 Conventionally, display of characters and graphics on packaging materials, labels, caps, films, containers, etc. has been performed by plate systems such as gravure printing method, flexographic printing method, offset printing method and silk screen printing method. Also, stamp printing, ink jet printing, thermal transfer ribbon method, engraving printing, and the like are performed.
しかし、このような印字方法では印刷インキ、感熱インキ等が対象物の表面に印字される方法であることから、識別の記号、番号、文字、図形自体が引っ掻き、油等により消字する問題があり、安全性の表示、トレーサビリテイの点でも大きな問題であった。
そこで、本発明は透明プラスチックフイルム(1)、印刷インキから形成されたインキ皮膜層(2)とフィルム、紙、或いは金属箔等の基材(3)からなるレーザマーキング用積層体にレーザ照射し、引っ掻き、油との接触でも消えない文字、図形、コード類をマーキングできる安価なレーザマーキング用積層体を提供することを目的とする。 Therefore, the present invention applies laser irradiation to a laminate for laser marking comprising a transparent plastic film (1), an ink film layer (2) formed from printing ink, and a substrate (3) such as a film, paper, or metal foil. An object of the present invention is to provide an inexpensive laser marking laminate capable of marking characters, figures and codes that do not disappear even when scratched or contacted with oil.
即ち、本発明は、透明プラスチックフイルム(1)、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)、および基材(3)からなるレーザマーキング用積層体であって、
塩酢ビ樹脂を含有する印刷インキが、
白色顔料もしくは黄色顔料
の少なくともいずれかを含有し、かつ、
ウレタン樹脂
を含有し、さらに
印刷インキの固形分100重量部中、塩酢ビ樹脂を、20〜90重量部
含有し、さらに、
レーザ照射で発色する発色剤
を含有しすることを特徴とするレーザマーキング用積層体に関するものである。
That is, the present invention is a laser marking laminate comprising a transparent plastic film (1), an ink film layer (2) formed from a printing ink containing a vinyl chloride resin, and a substrate (3) ,
Printing ink containing vinyl chloride resin is
White or yellow pigment
And containing at least one of
Urethane resin
Contains
20 to 90 parts by weight of vinyl chloride resin in 100 parts by weight of solid content of printing ink
Contains, and
Color former that develops color by laser irradiation
It is related with the laminated body for laser marking characterized by containing .
さらに、本発明は、発色剤が銅・モリブデン複合酸化物であることを特徴とする上記のレーザマーキング用積層体に関するものである。 Furthermore, the present invention relates to the above-mentioned laminate for laser marking, wherein the color former is a copper / molybdenum composite oxide.
また、本発明は、基材(3)が紙、アルミ箔、またはプラスチックフイルムのいずれかであることを特徴とする上記のレーザマーキング用積層体に関するものである。 The present invention also relates to the above-described laminate for laser marking, wherein the substrate (3) is any one of paper, aluminum foil, and plastic film.
さらに、本発明は、食品用軟包装体であることを特徴とする上記のレーザマーキング用積層体に関するものである。 Furthermore, this invention relates to said laminated body for laser marking characterized by being a soft packaging body for foodstuffs.
また、本発明は、上記のレーザマーキング用積層体にレーザ照射し、文字、図形、またはコードをマーキングすることを特徴とするレーザマーキング方法に関するものである。 The present invention also relates to a laser marking method characterized in that the laser marking laminate is irradiated with laser to mark characters, figures, or codes.
さらに、本発明は、食品用軟包装体のヒートシール部にマーキングすることを特徴とする上記のレーザマーキング方法に関するものである。 Furthermore, this invention relates to said laser marking method characterized by marking to the heat seal part of the soft packaging body for foodstuffs.
また、本発明は、賞味期限、ロット番号またはシリアル番号のいずれかをマーキングすることを特徴とする上記のレーザマーキング方法に関するものである。 The present invention also relates to the laser marking method described above, wherein any one of an expiration date, a lot number, or a serial number is marked.
さらに、本発明は、炭酸ガス、YAGレーザまたはYVO4レーザのいずれかを用いてマーキングすることを特徴とする上記のレーザマーキング方法に関するものである。 Furthermore, the present invention relates to the laser marking method described above, wherein marking is performed using any one of carbon dioxide, YAG laser, and YVO4 laser.
また、本発明は、上記の方法により得られることを特徴とするレーザマーキングされた積層体に関するものである。 The present invention also relates to a laser-marked laminate obtained by the above method.
本態様のレーザマーキング用積層体は、表面に透明プラスチックフイルム(1)を有しており、レーザ光照射により、積層体内部の印刷インキから形成されたインキ皮膜層(2)に、直接文字、図形、コード類をマーキングすることが可能である。また、表面保護層として透明プラスチックフイルム(1)を有していることから、印字後の後加工なしに、優れた耐水性、耐油性、耐摩耗性も付与できる。 The laminate for laser marking according to this aspect has a transparent plastic film (1) on the surface, and is directly applied to the ink film layer (2) formed from the printing ink inside the laminate by irradiation with laser light. It is possible to mark figures and codes. In addition, since the transparent plastic film (1) is provided as the surface protective layer, excellent water resistance, oil resistance, and abrasion resistance can be imparted without post-processing after printing.
レーザマーキング用積層体を包装体、もしくはラベルとして使用し、文字、図形、コードを記録すると商品、製品の流通管理、拡販において、印字が消えないことから、その識別機能を十分に発揮することができる。 If the laser marking laminate is used as a package or label and characters, figures, and codes are recorded, printing will not be erased in merchandise and product distribution management and sales expansion. it can.
本発明のレーザマーキング用積層体の基本構成としては、透明プラスチックフイルム(1)、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)、基材(3)である。具体的な積層体の構成は、例えばA)透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/アンカーコート層/プラスチックフイルム(3)、B)透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/印刷インキ皮膜層/接着剤層/プラスチックフイルム(3)、C)透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/印刷インキ皮膜層/接着剤層/アルミ箔(3)等がある。レーザマーキング用積層体を包装体として使用する場合、基材(3)はヒートシール性を有するプラスチックフイルムであることが好ましい。 The basic structure of the laser marking laminate of the present invention is a transparent plastic film (1), an ink film layer (2) formed from printing ink containing a vinyl acetate resin, and a substrate (3). The specific structure of the laminate is, for example, A) a transparent plastic film (1) / an ink film layer (2) formed from a printing ink containing a vinyl acetate resin / an anchor coat layer / a plastic film (3), B ) Transparent plastic film (1) / Ink film layer formed from printing ink containing vinyl chloride resin (2) / Printing ink film layer / Adhesive layer / Plastic film (3), C) Transparent plastic film (1 ) / Ink film layer (2) / printing ink film layer / adhesive layer / aluminum foil (3) formed from printing ink containing vinyl chloride resin. When the laminate for laser marking is used as a package, the substrate (3) is preferably a plastic film having heat sealability.
レーザによる発色は、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)内で行われる。塩酢ビ樹脂を用いるとレーザを照射した時、黒色化、炭化が起こりやすく、他の樹脂に比べて印字濃度が高くなる。塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)は塩酢ビ樹脂を有する印刷インキより形成され、該印刷インキには必要に応じて、インキ適性、印刷適性、印刷効課などを向上させる目的で各種の添加剤などを添加することができる。 Color development by laser is performed in an ink film layer (2) formed from a printing ink containing a vinyl chloride resin. When a vinyl chloride resin is used, when irradiated with a laser, blackening and carbonization are likely to occur, and the printing density becomes higher than other resins. The ink film layer (2) formed from the printing ink containing the vinyl chloride resin is formed from the printing ink having the vinyl chloride resin, and the printing ink has ink suitability, print suitability, printing effect as required. Various additives and the like can be added for the purpose of improving the section.
添加剤としては、顔料分散剤、消泡剤、レベリング剤、ワックス、シランカップリング剤、防腐剤、防錆剤、可塑剤、難燃剤、顕色剤などを挙げることができる。これら添加剤の種類、使用量は、印刷方法、印刷基材、印刷条件により適宜選択できる。 Examples of the additives include pigment dispersants, antifoaming agents, leveling agents, waxes, silane coupling agents, preservatives, rust inhibitors, plasticizers, flame retardants, and color developers. The type and amount of these additives can be appropriately selected depending on the printing method, printing substrate, and printing conditions.
通常のレーザマーキングでは、印字濃度向上のためレーザ光を吸収性する発色剤をあらたに添加する場合が多い。本発明の塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜(2)を使用すると、塩酢ビ樹脂が発色性に優れ、また安価であることから、より低コストで印字濃度の高いレーザマーキングを行うことができる。 In ordinary laser marking, a color former that absorbs laser light is often newly added to improve the printing density. When the ink film (2) formed from the printing ink containing the vinyl chloride resin of the present invention is used, since the vinyl chloride resin is excellent in color developability and inexpensive, the printing density is low and the printing density is high. Laser marking can be performed.
本態様のレーザマーキング用積層体は、積層体の内部に直接印字し、後でマーキングを変更できない。また、レーザ印字場所、字、図形、コード類の大きさによっては第3者が、その存在、或いはその内容を認識しがたいので偽造防止の機能も発揮できる。 The laser marking laminate of this embodiment prints directly inside the laminate, and the marking cannot be changed later. In addition, depending on the size of the laser printing place, characters, figures, and codes, it is difficult for a third party to recognize the presence or contents of the third party, so that the function of preventing forgery can be exhibited.
塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)には、塩酢ビ樹脂の他、顔料を必要に応じて併用することにより視認性の高いレーザ発色性有する積層体を得ることができる。とりわけ白色顔料、黄色顔料を用いると視認性の優れた印字物が得られる。白色顔料としては酸化チタンがあり、アナターゼ、ルチル型共に使用できる。黄色顔料としは、ファストイエローG、ファストイエロー10G、ファストイエローFGL、ジスアゾイエローAAA、ジスアゾイエローAAOT、ジスアゾイエローAAMX、イソインドリノンイエローG、ベンズイミダゾロンイエローH2Q等が挙げられる。 For the ink film layer (2) formed from the printing ink containing the vinyl chloride resin, in addition to the vinyl chloride resin, a layered product having high visibility of laser coloration can be obtained by using a pigment in combination as required. Obtainable. In particular, when a white pigment or a yellow pigment is used, a printed matter with excellent visibility can be obtained. There is titanium oxide as a white pigment, and both anatase and rutile types can be used. Examples of the yellow pigment include Fast Yellow G, Fast Yellow 10G, Fast Yellow FGL, Disazo Yellow AAA, Disazo Yellow AAOT, Disazo Yellow AAMX, Isoindolinone Yellow G, Benzimidazolone Yellow H2Q, and the like.
塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)をなす塩酢ビ樹脂を有する印刷インキには、印刷インキ固形分100重量部中に塩酢ビ樹脂が20〜90重量部含まれていることが、印刷インキ皮膜層のレーザ印字濃度と皮膜強度、凝集力とのバランスの点で好ましい。特に好ましくは、30〜80重量部である。20量部未満では印字濃度が劣り、また、90重量部を超えると、印字濃度はあるものの、フイルム等に対して接着性が低下する。 The printing ink having the vinyl chloride resin forming the ink film layer (2) formed from the printing ink containing the vinyl chloride resin contains 20 to 90 wt.% Of the vinyl chloride resin in 100 parts by weight of the printing ink solid content. It is preferable that it is contained in part in terms of the balance between the laser printing density of the printing ink film layer, the film strength, and the cohesive force. Particularly preferred is 30 to 80 parts by weight. If the amount is less than 20 parts by weight, the print density is inferior. If the amount exceeds 90 parts by weight, the adhesiveness to a film or the like is lowered although there is a print density.
本発明において塩酢ビ樹脂とは、塩化ビニル−酢酸ビニル共重合体の樹脂を表し、塩化ビニルと酢酸ビニルのモル比、重合度、分子量により、耐薬品性、強靭性、接着性、溶解性等が変わる。なお、インキの種類、印刷方法、印刷構成等から適宜塩酢ビ樹脂を選択することができる。市販の塩酢ビ樹脂としては、例えばSOLBIN C,CL、CH,CN、C5R,A,AL,TA2,TA3,TAO,TA5R、M、ME,MFK(日信化学工業株式会社製)、VINNOL E14/45,H14/36,H40/55,E15/45M(Wacker社製)等が挙げられるが、これらに限定されるものではない。 In the present invention, the vinyl chloride resin represents a vinyl chloride-vinyl acetate copolymer resin. Depending on the molar ratio of vinyl chloride and vinyl acetate, the degree of polymerization, and the molecular weight, chemical resistance, toughness, adhesiveness, solubility Etc. change. In addition, a vinyl acetate resin can be selected suitably from the kind of ink, a printing method, a printing structure, etc. Examples of commercially available vinyl chloride resin include SOLBIN C, CL, CH, CN, C5R, A, AL, TA2, TA3, TAO, TA5R, M, ME, MFK (manufactured by Nissin Chemical Industry Co., Ltd.), VINNOL E14. / 45, H14 / 36, H40 / 55, E15 / 45M (manufactured by Wacker) and the like, but are not limited thereto.
塩酢ビ樹脂を含有する印刷インキには、当該樹脂の他、アクリル樹脂、アクリル変性ウレタン樹脂、スチレン/アクリル樹脂、エチレン/アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、ロジン変性マレイン酸樹脂、ポリビニルアセタール樹脂、ポリアマイド樹脂、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロース等のセルロース系樹脂等を併用することができる。 Printing inks containing vinyl chloride resin include acrylic resin, acrylic modified urethane resin, styrene / acrylic resin, ethylene / acrylic resin, urethane resin, polyester resin, rosin modified maleic acid resin, polyvinyl acetal resin in addition to the resin. , Cellulose resins such as polyamide resin, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, and the like can be used in combination.
塩酢ビ樹脂以外のこれらの樹脂の中で、ウレタン樹脂を塩酢ビ樹脂と併用させるとフイルムへの密着性、熱的緩和性が向上し、レーザマーキング用積層体として好適に用いることができる。特にレーザマーキング用積層体を食品用軟包装体として使用する場合、ウレタン樹脂と塩酢ビ樹脂を併用することで、レーザ印字濃度が良好で、接着性、ラミネート強度、ヒートシール強度が優れたボイル、レトルト用包装体が得られる。 Among these resins other than vinyl chloride resin, when a urethane resin is used in combination with vinyl chloride resin, adhesion to the film and thermal relaxation are improved, and it can be suitably used as a laminate for laser marking. . In particular, when using the laser marking laminate as a soft food packaging, a combination of urethane resin and vinyl acetate resin makes it possible to achieve good laser printing density, boil with excellent adhesion, laminate strength, and heat seal strength. A package for retort is obtained.
本態様のレーザマーキング用積層体では、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)が、透明プラスチックフイルム(1)および基材(3)で挟まれて存在する。このため、印字時および使用中において印字面の剥離、飛散、摩耗等を防ぐことが可能となる。 In the laminate for laser marking of this embodiment, an ink film layer (2) formed from a printing ink containing a vinyl acetate resin is sandwiched between a transparent plastic film (1) and a substrate (3). For this reason, it is possible to prevent peeling, scattering, abrasion, and the like of the printed surface during printing and during use.
透明プラスチックフイルム(1)、または基材(3)上に塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)を設ける方法は、特に限定されず、印刷方式の他、インクジェット、浸漬、スピンコーティング等が挙げられる。好ましくはグラビア印刷、オフセット印刷、フレキソ印刷、シルクスクリーン印刷により積層する方法である。 The method of providing the ink film layer (2) formed of the transparent plastic film (1) or the printing ink containing the vinyl chloride resin on the base material (3) is not particularly limited, and in addition to the printing method, inkjet , Immersion, spin coating and the like. A method of laminating by gravure printing, offset printing, flexographic printing or silk screen printing is preferred.
塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)は塩酢ビ樹脂を含有する印刷インキ、塗工液より形成され、好ましくは印刷インキである。塩酢ビ樹脂を含有する印刷インキは、塩酢ビ樹脂の他にレーザ照射により発色する発色剤を含んでもよい。レーザ発色性を有する発色剤としては、無機材料、有機材料がある。本態様に用いられる無機材料は、例えば、1)金属単体、2)金属塩、3)金属水酸化物、4)金属の酸化物等を示す。 The ink film layer (2) formed from the printing ink containing the vinyl chloride resin is formed from the printing ink and the coating liquid containing the vinyl chloride resin, and is preferably printing ink. The printing ink containing a vinyl chloride resin may contain a color former that develops color by laser irradiation in addition to the vinyl chloride resin. Examples of the color former having laser colorability include inorganic materials and organic materials. The inorganic material used in this embodiment is, for example, 1) a simple metal, 2) a metal salt, 3) a metal hydroxide, 4) a metal oxide, or the like.
1)金属の単体としては、鉄、亜鉛、スズ、ニッケル、銅、銀、金等が挙げられる。 1) Examples of simple metals include iron, zinc, tin, nickel, copper, silver, and gold.
2)金属の塩としては、炭酸銅、炭酸ニッケル、炭酸マンガン、炭酸コバルト、炭酸ランタン、硝酸マグネシウム、硝酸マンガン、硝酸鉄、硝酸カドミウム、硝酸亜鉛、硝酸コバルト、硝酸鉛、硝酸ニッケル、硝酸銅、硝酸パラジウム、硝酸ランタン、酢酸マグネシウム、酢酸マンガン、酢酸カドミウム、酢酸亜鉛、酢酸コバルト、酢酸鉛、酢酸ニッケル、酢酸銅、酢酸パラジウム、塩化銅、塩化鉄、塩化コバルト、塩化ニッケル、塩化銀、塩化亜鉛、リン酸銅、リン酸鉄、リン酸コバルト、ピロリン酸銅、硫酸銅、硫酸鉄、硫酸コバルト、シュウ酸銅、シュウ酸鉄、シュウ酸コバルト、安息香酸銅、安息香酸鉄、安息香酸コバルト、芳香環を有するホスホン酸銅などが挙げられる。 2) Metal salts include copper carbonate, nickel carbonate, manganese carbonate, cobalt carbonate, lanthanum carbonate, magnesium nitrate, manganese nitrate, iron nitrate, cadmium nitrate, zinc nitrate, cobalt nitrate, lead nitrate, nickel nitrate, copper nitrate, Palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, lead acetate, nickel acetate, copper acetate, palladium acetate, copper chloride, iron chloride, cobalt chloride, nickel chloride, silver chloride, zinc chloride , Copper phosphate, iron phosphate, cobalt phosphate, copper pyrophosphate, copper sulfate, iron sulfate, cobalt sulfate, copper oxalate, iron oxalate, cobalt oxalate, copper benzoate, iron benzoate, cobalt benzoate, Examples thereof include copper phosphonate having an aromatic ring.
3)金属の水酸化物としては、水酸化銅、水酸化アルミニウム、水酸化マグネシウム、水酸化亜鉛、水酸化アンチモン、水酸化コバルト、水酸化ニッケル、水酸化鉄、水酸化ランタン等が挙げられる。 3) Examples of the metal hydroxide include copper hydroxide, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, antimony hydroxide, cobalt hydroxide, nickel hydroxide, iron hydroxide, and lanthanum hydroxide.
4)金属の酸化物としては、酸化ケイ素、酸化アルミニウム、酸化鉄、酸化マグネシウム、酸化コバルト、酸化鉛、酸化スズ、酸化インジウム、酸化マンガン、酸化モリブテン、酸化ニッケル、酸化銅、酸化パラジウム、酸化ランタン、アンチモンドープ酸化スズ(ATO)、インジウムドープ酸化スズ(ITO)、合成ゼオライト、天然ゼオライト、銅−モリブテン複合酸化物(42−903A、東缶マテリアル・テクノロジー株式会社製)、酸化アンチモンドープ酸化スズ等被覆雲母(レーザフレア820,825、メルク株式会社製)等が挙げられる。 金属酸化物としては、層状構造を有する、マイカ、モンモリロナイト、スメクタイト等を用いることもできる。 4) Examples of metal oxides include silicon oxide, aluminum oxide, iron oxide, magnesium oxide, cobalt oxide, lead oxide, tin oxide, indium oxide, manganese oxide, molybdenum oxide, nickel oxide, copper oxide, palladium oxide, and lanthanum oxide. Antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), synthetic zeolite, natural zeolite, copper-molybten complex oxide (42-903A, manufactured by Tocan Material Technology Co., Ltd.), antimony oxide-doped tin oxide, etc. Covered mica (Laser Flare 820, 825, manufactured by Merck & Co., Inc.) and the like can be mentioned. As the metal oxide, mica, montmorillonite, smectite, etc. having a layered structure can also be used.
無機材料の中では、銅化合物、モリブデン化合物、鉄化合物、ニッケル化合物、クロム化合物、ジルコニウム化合物、またはアンチモン化合物から選ばれる1種以上の材料、より好ましくは、銅化合物、モリブデン化合物、クロム化合物、ニッケル化合物を有する材料、さらに好ましくは、銅−モリブデン複合酸化物などが挙げられる。特に、銅−モリブテン複合酸化物は自己発色性が強く、また銅−モリブデン複合酸化物自身の近傍の樹脂なども黒化させやすいため、視認性の優れた印字物が得られる。
レーザが照射されても無機材料自身の発色はなく、近傍のバインダー樹脂、添加剤などが炭化、分解、気化し発色する場合も有る。レーザ発色層を有する積層体にレーザ照射することで鮮明性、コントラスト、視認性に優れた文字、図形を有する包装体、ラベルが得られる。
Among inorganic materials, one or more materials selected from copper compounds, molybdenum compounds, iron compounds, nickel compounds, chromium compounds, zirconium compounds, or antimony compounds, more preferably copper compounds, molybdenum compounds, chromium compounds, nickel A material having a compound, more preferably, a copper-molybdenum composite oxide or the like can be given. In particular, the copper-molybten complex oxide has strong self-coloring properties, and the resin in the vicinity of the copper-molybdenum complex oxide itself can be easily blackened, so that a printed matter with excellent visibility can be obtained.
Even when irradiated with a laser, the inorganic material itself does not develop color, and the nearby binder resin, additive, and the like may carbonize, decompose, and vaporize to develop color. By irradiating the laminate having the laser coloring layer with a laser, a package and a label having characters and figures excellent in sharpness, contrast and visibility can be obtained.
塩酢ビ樹脂を含有する印刷インキ固形分100重量部中に、発色剤は1〜30重量部含まれていることが好ましく、特に好ましくは、5〜20重量部である。 It is preferable that 1 to 30 parts by weight of the color former is contained in 100 parts by weight of the printing ink solid content containing the vinyl chloride resin, and particularly preferably 5 to 20 parts by weight.
1重量部未満では皮膜としての凝集力はあるものの発色性が劣る。また、30重量部を超えると、皮膜の強度、凝集力が低下し、レーザ照射により積層体の折り曲げ耐性が低下し、場合によっては層間で剥離する。 If it is less than 1 part by weight, the color developability is inferior although the film has cohesive strength. On the other hand, when the amount exceeds 30 parts by weight, the strength and cohesive strength of the film are lowered, the bending resistance of the laminate is lowered by laser irradiation, and in some cases, the laminate peels off.
レーザ発色性を有する有機材料として染料も使用することが出来る。染料としては、特に制限はないが、積層体の使用目的、用途、使用環境に合わせて適宜選択可能である。染料として、特に通常の感熱記録において使用される公知の発色剤や顕色剤を使用すれば視認性の高い印字物を得ることができる。 A dye can also be used as an organic material having laser colorability. Although there is no restriction | limiting in particular as dye, It can select suitably according to the intended purpose, use, and use environment of a laminated body. A print with high visibility can be obtained by using, as the dye, a known color former or developer used in ordinary thermal recording.
例えば発色剤としては通常の感熱記録において電子供与体として使われている発色性化合物が使用できる。例えば、フルオラン系、フェノチアジン系、スピロピラン系、トリフェニルメタフタリド系、ローダミンラクタム系等のロイコ染料が挙げられる。ロイコ染料の具体例としては、3,3−ビス(p−ジメチルアミノフェニル)フタリド、3,3−ビス(p−ジメチルアミノフェニル)−6−ジメチルアミノフタリド、3,3−ビス(p−ジメチルアミノフェニル)−6−アミノフタリド、3,3−ビス(p−ジメチルアミノフェニル)−6−ニトロフタリド、3,3−ビス(p−ジメチルアミノフェニル)フタリド、3,3−ビス(3−ジメチルアミノ)−7−メチルフルオラン、3−ジエチルアミノ−7−クロロフラン、3−ジエチルアミノ−6−クロロ−7−メチルフルオラン、3−ジエチルアミノ−7−アニリノフルオラン、3−ジエチルアミノ−6−メチル−7−アニリノフルオラン、3−ピペリジノ−6−メチル−7−アニリノフルオラン等が挙げられる。 For example, as the color former, a color developable compound used as an electron donor in ordinary thermal recording can be used. For example, leuco dyes such as fluorane, phenothiazine, spiropyran, triphenylmethphthalide, rhodamine lactam and the like can be mentioned. Specific examples of the leuco dye include 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and 3,3-bis (p- Dimethylaminophenyl) -6-aminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-nitrophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (3-dimethylamino) ) -7-methylfluorane, 3-diethylamino-7-chlorofuran, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-6-methyl- Examples include 7-anilinofluorane and 3-piperidino-6-methyl-7-anilinofluorane.
顕色剤は通常、発色剤と共に用いられる。
顕色剤としては、感熱記録体において電子受容体として使用される物質、例えばフェノール系化合物である4−フェニルフェノール、4−ヒドロキシアセトフェノン、2,2−ジヒドロキシジフェニル、2,2−メチレンビス(4−クロロフェノール)、2,2−メチレンビス(4−メチル−6−t−ブチルフェノール)、4,4−イソプロピリデンジフェノール、4,4−イソプロピリデンビス(2−クロロフェノール)、4,4−イソプロピリデンビス(2−メチルフェノール)、4,4−エチレンビス(2−メチルフェノール)等、その他酸性白土カオリン、ゼオライト、芳香族カルボン酸、その無水物、有機スルホン酸を用いることができる。なかでもフェノール系化合物が好ましい。
The developer is usually used together with a color former.
As the developer, a substance used as an electron acceptor in a heat-sensitive recording material, such as 4-phenylphenol, 4-hydroxyacetophenone, 2,2-dihydroxydiphenyl, 2,2-methylenebis (4- Chlorophenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 4,4-isopropylidenediphenol, 4,4-isopropylidenebis (2-chlorophenol), 4,4-isopropylidene Bis (2-methylphenol), 4,4-ethylenebis (2-methylphenol), and other acidic clay kaolin, zeolite, aromatic carboxylic acid, its anhydride, and organic sulfonic acid can be used. Of these, phenol compounds are preferred.
上記発色剤と顕色剤の比率は、発色剤1重量部に対して、顕色剤2〜10重量部が好ましい。また、上記の染料系発色剤と顕色剤の合計が塩酢ビ樹脂を含有する印刷インキ固形分100重量部中で占める割合は5〜50重量%であることが好ましい。 The ratio of the color former to the developer is preferably 2 to 10 parts by weight with respect to 1 part by weight of the color developer. Moreover, it is preferable that the ratio which the sum total of said dye type color former and a color developer occupies in 100 weight part of printing ink solid content containing a vinyl acetate resin is 5 to 50 weight%.
ロイコ染料はレーザの熱による発色性が良好なことから、好適に用いられる。本態様において、特に染料を用いる場合は、積層体に表面保護層があっても、染料が溶出する可能性があるため、製品の製造工程でボイル、レトルト等がないことが好ましい。 A leuco dye is preferably used because it has good color developability by laser heat. In this embodiment, particularly when a dye is used, it is preferable that there is no boil or retort in the manufacturing process of the product because the dye may be eluted even if the laminate has a surface protective layer.
次に少なくとも透明プラスチックフイルム(1)、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)、および基材(3)からなるレーザマーキング用積層体の製造工程について一例を説明する。 Next, an example of the manufacturing process of a laser marking laminate comprising at least a transparent plastic film (1), an ink film layer (2) formed from a printing ink containing a vinyl acetate resin, and a substrate (3) will be described. To do.
塩酢ビ樹脂を有する印刷インキの調整としては、以下のようである。
塩酢ビ樹脂に、必要に応じて顔料、溶剤を混合し、分散機にて均一化する。次に必要に応じて各種添加剤を混合、攪拌し、溶剤等で粘度調整を行う。
The adjustment of the printing ink having the vinyl chloride resin is as follows.
If necessary, the vinyl chloride resin is mixed with a pigment and a solvent and homogenized with a disperser. Next, if necessary, various additives are mixed and stirred, and the viscosity is adjusted with a solvent or the like.
分散機としては、ペイントコンディショナー(レッドデビル社製)、ボールミル、サンドミル(シンマルエンタープライゼス社製「ダイノーミル」等)、アトライター、パールミル(アイリッヒ社製「DCPミル」等)、コボールミル、ホモミキサー、ホモジナイザー(エム・テクニック社製「クレアミックス」等)、湿式ジェットミル(ジーナス社製「ジーナスPY」、ナノマイザー社製「ナノマイザー」)等が挙げられる。分散機にメディアを使う場合には、ガラスビーズ、ジルコニアビーズ、アルミナビーズ、磁性ビーズ、スチレンビーズ等を用いることが好ましい。 Dispersers include paint conditioners (manufactured by Red Devil), ball mills, sand mills (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritors, pearl mills (such as “DCP mill” manufactured by Eirich), coball mills, homomixers, Examples thereof include a homogenizer (such as “CLEARMIX” manufactured by M Technique Co., Ltd.), a wet jet mill (“GENUS PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer), and the like. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like.
溶剤としては、印刷用に用いられる公知の溶剤を用いることが可能であり、例えば、エタノール、イソプロピルアルコール、酢酸メチル、メチルイソブチルケトン、1−メトキシー2−プロパノール、トルエン、キシレンなどが挙げられる。また、水性印刷インキでは水、必要に応じてアルコール等を併用する。 As the solvent, a known solvent used for printing can be used, and examples thereof include ethanol, isopropyl alcohol, methyl acetate, methyl isobutyl ketone, 1-methoxy-2-propanol, toluene, and xylene. In the case of water-based printing ink, water, alcohol or the like is used in combination.
本態様に用いられる基材(3)としては、プラスチックフイルム、紙、アルミ箔が挙げられる。プラスチックフイルムとしては低密度ポリエチレン、無延伸および延伸ポリプロピレン、ポリエステル、ナイロン、ポリスチレン、ポリ塩化ビニル、ポリカーボネイト、ポリビニルアルコールフイルム等、及びポリ塩化ビニリデン等をコーテイングしたポリプロピレン、ポリエステル、ナイロン、セロファン等のフイルムも挙げられる。また、蒸着フイルム、例えばシリカなどを蒸着したPETフイルムも用いることができる。紙としてはアート紙、コート紙、上質紙、和紙、合成紙等、アルミ箔としては印刷に適した厚みのもの、アルミを蒸着したものも使用できる。また、基材として剥離紙を使用し、更に粘着剤層を設けると、本発明の積層体はラベルとしも使用できる。 As a base material (3) used for this aspect, a plastic film, paper, and aluminum foil are mentioned. Plastic films such as low density polyethylene, unstretched and stretched polypropylene, polyester, nylon, polystyrene, polyvinyl chloride, polycarbonate, polyvinyl alcohol film, and polyvinylidene chloride coated polypropylene, polyester, nylon, cellophane, etc. Can be mentioned. Further, a vapor deposition film, for example, a PET film vapor-deposited with silica or the like can also be used. Art paper, coated paper, high quality paper, Japanese paper, synthetic paper, etc. can be used as paper, and aluminum foil having a thickness suitable for printing or aluminum vapor deposited can be used. Moreover, when a release paper is used as a substrate and a pressure-sensitive adhesive layer is further provided, the laminate of the present invention can also be used as a label.
基材(3)の厚みは特に限定されない。プラスチックフイルムの場合、通常印刷に用いられるフイルムがそのまま適用できる。例えばPETの場合、12〜40μm、OPPの場合は20〜50μmが好適に用いられる。 The thickness of the substrate (3) is not particularly limited. In the case of a plastic film, the film normally used for printing can be applied as it is. For example, in the case of PET, 12 to 40 μm and in the case of OPP, 20 to 50 μm are preferably used.
レーザマーキング用積層体の製造においては、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)の上に、更に印刷インキ層を設けることも可能である。この印刷インキ層は、塩酢ビ樹脂を含有する印刷インキより形成されるものでも良く、また、別の色相の異なるインキ層、樹脂が異なるインキ層でも良い。 In the production of the laser marking laminate, it is also possible to provide a printing ink layer on the ink film layer (2) formed from the printing ink containing a vinyl acetate resin. This printing ink layer may be formed from a printing ink containing a vinyl chloride resin, or may be another ink layer having a different hue or an ink layer having a different resin.
塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)の厚さは、好ましくは0.1〜3μm/層である。 The thickness of the ink film layer (2) formed from the printing ink containing a vinyl chloride resin is preferably 0.1 to 3 μm / layer.
塩酢ビ樹脂を含有する印刷インキが顔料を含有しているとレーザ光照射においてレーザ光の透過の割合が低下し、塩酢ビ樹脂の発色性が向上するため、好ましくは白色顔料、黄色顔料等を添加することである。また、これら顔料を添加することで併せてレーザ印字自体のバックグランドとなり、印字がより鮮明になる。 If the printing ink containing the vinyl chloride resin contains a pigment, the ratio of laser beam transmission decreases upon laser light irradiation, and the color developability of the vinyl chloride resin is improved. Etc. are added. Further, by adding these pigments, it becomes a background of laser printing itself, and the printing becomes clearer.
塩酢ビ樹脂を含有する印刷インキ皮膜層(2)の膜強度、耐熱性、耐水性、耐溶剤性等の向上を目的に硬化剤を併用することができる。硬化剤としてはイソシアネート系、オキサゾリン系、カルボジイミド系、エチレンイミン系等が使用できる。膜強度、膜物性の点からはイソシネート系硬化剤が好ましい。イソシアネート系硬化剤の中でも3官能以上のものが特に良好である。 A curing agent can be used in combination for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance and the like of the printing ink film layer (2) containing a vinyl chloride resin. As the curing agent, isocyanate, oxazoline, carbodiimide, ethyleneimine, and the like can be used. From the viewpoint of film strength and film physical properties, isocyanate-based curing agents are preferred. Of the isocyanate curing agents, those having 3 or more functional groups are particularly good.
このようにして、得られたレーザマーキング用積層体の一部、或いは全面にマーキングを施した場合、積層体の内部にレーザ印字層が存在しているので、従来の印刷物で問題となっていた印字の剥離、傷つきをなくすができ、また油、水分との接触による字のかすれを無くすることもできる。 Thus, when marking was performed on a part or the entire surface of the obtained laminate for laser marking, a laser printing layer was present inside the laminate, which caused a problem with conventional printed matter. It can eliminate printing peeling and scratches, and can also eliminate blurring of characters due to contact with oil and moisture.
レーザ照射は、一般に透明プラスチックフイルム(1)側から行われる。ただし、基材(3)が透明な場合、レーザ照射は透明プラスチック(1)側だけではなく、基材(3)側からも可能な場合がある。この場合、塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)と基材(3)との間に着色した別のインキ層がないことが好ましい。 Laser irradiation is generally performed from the transparent plastic film (1) side. However, when the substrate (3) is transparent, laser irradiation may be possible not only from the transparent plastic (1) side but also from the substrate (3) side. In this case, it is preferable that there is no separate ink layer colored between the ink film layer (2) formed from the printing ink containing a vinyl acetate resin, and a base material (3).
レーザによる印字は、英数字、ひらがな、漢字等で目的とする内容を表示する他、バーコード、或いは2次元バーコードとして、更に多量の各種情報を書き込むことも可能である。2次元コードとしては、QR(モデル1)、QR(モデル2)、マイクロQR、DataMatrix等がある。また、写真、図形をパソコンを通して取り込み描画することも可能である。 In addition to displaying the desired contents in alphanumeric characters, hiragana, kanji, etc., laser printing can write a larger amount of various information as a barcode or a two-dimensional barcode. As the two-dimensional code, there are QR (model 1), QR (model 2), micro QR, DataMatrix, and the like. It is also possible to capture and draw photos and figures through a personal computer.
次いで、レーザ印字方法について説明する。本態様に好適に使用できるレーザとしては、例えば炭酸ガスレーザ(10640nm)、YAGレーザ(1064nm)、YVO4レーザ(1064nm)等が挙げられる。好ましくは、YAGレーザ、YVO4レーザである。更に好ましくはYVO4レーザであり、レーザ光の強度分布がシングルモードのパワー分布であることからより精細な印字が可能となる。 Next, a laser printing method will be described. Examples of the laser that can be suitably used in this embodiment include a carbon dioxide laser (10640 nm), a YAG laser (1064 nm), and a YVO4 laser (1064 nm). A YAG laser and a YVO4 laser are preferable. More preferably, it is a YVO4 laser, and since the intensity distribution of the laser beam is a single mode power distribution, finer printing is possible.
YAGレーザ、若しくはYVO4レーザの照射による印字品質は、1)LD%、2)Q−スイッチ周波数、及び3)走査速度の選択に依存する。 The print quality by irradiation with YAG laser or YVO4 laser depends on selection of 1) LD%, 2) Q-switch frequency, and 3) scanning speed.
LD%は、レーザー出力を表す。LD%によりレーザーパワーを制御できるが、大きくし過ぎると積層体がダメージを受けやすい。また、小さすぎると印字が不鮮明になる。Q−スイッチ周波数は、パルスを発生させる周波数を表す。Q−スイッチ周波数も印字品質に影響を及ぼし、大きすぎても、小さすぎても印字性が低下する。走査速度は印字ドットの間隔、印字時間等を制御するもので遅過ぎると印字ドットが集中し、場合によっては積層体がダメージを受ける。また、早過ぎるとと、印字ドット間が広くなり場合によっては印字濃度、印字品質の低下がみられる。 LD% represents the laser output. Laser power can be controlled by LD%, but if it is too large, the laminate is easily damaged. If it is too small, the print becomes unclear. The Q-switch frequency represents the frequency at which pulses are generated. The Q-switch frequency also affects the print quality, and if it is too large or too small, the printability is degraded. The scanning speed controls the interval between printing dots, printing time, etc. If the scanning speed is too slow, the printing dots are concentrated, and the laminate is damaged in some cases. On the other hand, if it is too early, the space between the print dots becomes wide, and in some cases, the print density and the print quality are lowered.
本発明のレーザマーキング用積層体を食品用軟包装体として用いれば、賞味期限、ロット番号、もしくはシリアル番号のマーキングが可能となり、トレーサビリテイ、安全・安心の観点から有用である。また、レーザマーキングを食品用軟包装体のヒートシール部へ施すことにより、より強いレーザ照射条件で印字することが可能となり、印字濃度、視認性の向上した包装体が得られる。 If the laminate for laser marking of the present invention is used as a soft package for foods, the expiration date, lot number, or serial number can be marked, which is useful from the viewpoint of traceability, safety and security. Further, by applying laser marking to the heat seal portion of the soft food packaging body, printing can be performed under stronger laser irradiation conditions, and a packaging body with improved printing density and visibility can be obtained.
本発明のレーザマーキング用積層体はラベルにも有用で、バーコードラベル、商品表示ラベル等、或いは類似の機能を有する荷物用タッグ、ワッペン、シール、ステッカー等に利用できる。 The laminate for laser marking of the present invention is also useful for labels, and can be used for bar code labels, product display labels, etc., or luggage tags, patches, seals, stickers, etc. having similar functions.
ラベルの基本構成として、A)透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/粘着剤層/剥離紙(3)、B)透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/基材(3)/粘着剤層/剥離紙等がある。粘着剤層は、天然ゴム、合成ゴム、ポリイソブチレン、2−エチルヘキシルアクリレート/n−ブチルアクリレート等を用いたアクリル樹脂、ポリエステル樹脂等の塗工液を塗工、乾燥した塗膜で形成される。塗工液には必要応じて、アビエチン酸ロジンエステル、テルペン・フェノール共重合体等の粘着付与剤、イソシアネート系、エポキシ系硬化剤を併用することができる。 The basic structure of the label is as follows: A) transparent plastic film (1) / ink film layer (2) formed from printing ink containing vinyl chloride resin / adhesive layer / release paper (3), B) transparent plastic film (1) / Ink film layer (2) / substrate (3) / adhesive layer / release paper formed from printing ink containing vinyl chloride resin. The pressure-sensitive adhesive layer is formed of a coating film obtained by applying and drying a coating liquid such as an acrylic resin or a polyester resin using natural rubber, synthetic rubber, polyisobutylene, 2-ethylhexyl acrylate / n-butyl acrylate, or the like. If necessary, a tackifier such as abietic acid rosin ester, a terpene / phenol copolymer, an isocyanate-based, and an epoxy-based curing agent can be used in the coating solution.
剥離紙としては、紙基材にシリコーン系、フッ素系剥離剤を塗付した離型紙、ポリオレフイン系樹脂を被覆したラミネート紙等が利用できる。 As the release paper, a release paper obtained by applying a silicone-based or fluorine-based release agent to a paper base, a laminated paper coated with a polyolefin resin, or the like can be used.
レーザ照射は、ラベルを対象とするものに貼付する前、或いは貼付した後でも可能である。 Laser irradiation can be performed before or after affixing to a target label.
以下、実施例に基づき本態様をさらに詳しく説明する。実施例中、部は重量部を表し、%は、重量%を表す。 Hereinafter, this embodiment will be described in more detail based on examples. In the examples, parts represent parts by weight, and% represents% by weight.
[ウレタン樹脂の合成]
(合成例1)
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコにポリテトラメチレングリコール(分子量2000、分子量はゲルパーミエーションクロマトグラフイで測定される数平均分子量を示す)1000部とイソホロンジイソシアネート222部を仕込み、窒素雰囲気下、85℃で5時間反応させた。次いで、40℃に冷却後イソホロンジアミン82部、ジ−n−ブチルアミン7.8部、メチルエチルケトン2488部およびイソプロピルアルコール573部を添加し、攪拌下40℃で5時間反応させた。このようにして得られたウレタン樹脂の固形分は30%であった。
[Synthesis of urethane resin]
(Synthesis Example 1)
1000 parts of polytetramethylene glycol (molecular weight 2000, molecular weight indicates number average molecular weight measured by gel permeation chromatography) in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube And 222 parts of isophorone diisocyanate were added and reacted at 85 ° C. for 5 hours in a nitrogen atmosphere. Subsequently, after cooling to 40 ° C., 82 parts of isophorone diamine, 7.8 parts of di-n-butylamine, 2488 parts of methyl ethyl ketone and 573 parts of isopropyl alcohol were added and reacted at 40 ° C. for 5 hours with stirring. The urethane resin thus obtained had a solid content of 30%.
[アクリル樹脂の合成]
(合成例2)
攪拌機、温度計、還流冷却器、および窒素ガス導入管を備えた四つ口フラスコにイソプロピルアルコール600部を仕込み、攪拌下、窒素雰囲気下で80℃迄昇温した。次に、予め調整しておいたアクリル酸20部、メタクリル酸2-ヒドロキシエチル58部、アクリル酸メチル20部、メタクリル酸メチル370部、アクリル酸ブチル130部およびアゾビスイソブチロニトリル12部の混合液を2時間で滴下した。滴下後1時間経て、アゾビスイソブチロニトリル2部を加え、更に2時間反応させた。反応終了後、メチルエチルケトンで固形分の調整を行った。このようにして得られたアクリル樹脂の固形分は30%、粘度は320cps(25℃)であった。
[Synthesis of acrylic resin]
(Synthesis Example 2)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 600 parts of isopropyl alcohol, and the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring. Next, 20 parts of acrylic acid prepared in advance, 58 parts of 2-hydroxyethyl methacrylate, 20 parts of methyl acrylate, 370 parts of methyl methacrylate, 130 parts of butyl acrylate and 12 parts of azobisisobutyronitrile were prepared. The mixture was added dropwise over 2 hours. One hour after the dropping, 2 parts of azobisisobutyronitrile was added, and the mixture was further reacted for 2 hours. After completion of the reaction, the solid content was adjusted with methyl ethyl ketone. The acrylic resin thus obtained had a solid content of 30% and a viscosity of 320 cps (25 ° C.).
[白色インキの製造]
(製造例1)
白色インキは、白顔料20部、合成例1で得たウレタン樹脂80部、メチルエチルケトン30部の混合物をペイントシェーカで練肉し、着色インキを得た。得られた着色インキを更に、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剤(重量比50:40:10)で希釈し、ザーンカープ#3(離合社製)で17秒(25℃)に調整し、重ね刷り用白色インキを得た。
[Manufacture of white ink]
(Production Example 1)
For the white ink, a mixture of 20 parts of white pigment, 80 parts of the urethane resin obtained in Synthesis Example 1 and 30 parts of methyl ethyl ketone was kneaded with a paint shaker to obtain a colored ink. The obtained colored ink was further diluted with a mixed solvent of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio 50:40:10), and adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Ransha Co., Ltd.) A white ink for overprinting was obtained.
(参考実施例1)
酸化チタン5部、塩酢ビ樹脂SOLBIN C60部(日信化学工業 MEK30%溶液に調整)、メチルエチルケトン50部の混合物をペイントシェーカで練肉し、塩酢ビ樹脂を有する印刷インキを得た。得られた印刷インキを更に、メチルエチルケトン、酢酸エチルの混合溶剤(重量比70:30)で希釈し、ザーンカープ#3(離合社製)で17秒(25℃)に調整し、印刷用の塩酢ビ樹脂を含有する印刷インキを得た。
( Reference Example 1)
A mixture of 5 parts of titanium oxide, 60 parts of vinyl chloride resin SOLBIN C (adjusted to a 30% solution of Nissin Chemical Industry MEK) and 50 parts of methyl ethyl ketone was kneaded with a paint shaker to obtain a printing ink having a vinyl chloride resin. The obtained printing ink was further diluted with a mixed solvent of methyl ethyl ketone and ethyl acetate (weight ratio 70:30), adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Hoshinsha), and salted vinegar for printing A printing ink containing a bi-resin was obtained.
透明プラスチックフイルム(1)としてコロナ放電処理PET(東洋紡績社製「エステルE5102」、膜厚12μm)の処理面側に、版深35μmのグラビア版を用いて印刷速度50m/分、乾燥温度60℃で印刷し、印刷物を得た。続いて製造例1で得られた白色インキを用いて同様な印刷条件で白色インキを重ね刷りした。
得られたPET印刷物を接着剤「TM250/CAT−RT80」(東洋モートン社製)を用いドライラミネーションにより低密度ポリエチレン「TUX−FCD」(トーセロ製、膜厚40μm)を貼り合わせた。得られたラミネート物は40℃で3日間エージングを施し、最終的に透明プラスチックフイルム(1)/塩酢ビ樹脂を含有する印刷インキより形成されたインキ皮膜層(2)/接着剤/ポリエチレン(3)を有するレーザマーキング用積層体を得た。
As a transparent plastic film (1), a corona discharge-treated PET (“Ester E5102” manufactured by Toyobo Co., Ltd., film thickness: 12 μm) is coated with a gravure plate having a plate depth of 35 μm, a printing speed of 50 m / min, and a drying temperature of 60 ° C. To obtain a printed matter. Subsequently, the white ink obtained in Production Example 1 was overprinted under the same printing conditions.
Low-density polyethylene “TUX-FCD” (manufactured by Tosero, film thickness of 40 μm) was bonded to the obtained PET printed matter by dry lamination using an adhesive “TM250 / CAT-RT80” (manufactured by Toyo Morton). The obtained laminate was aged at 40 ° C. for 3 days, and finally an ink film layer (2) / adhesive / polyethylene (formed from a printing ink containing a transparent plastic film (1) / vinyl acetate resin. A laminate for laser marking having 3) was obtained.
(参考実施例2〜5、実施例6、7、参考実施例8、9、比較例1、2)
表1に参考実施例2〜5、実施例6、7、参考実施例8、9、及び比較例1、2に用いた塩酢ビ樹脂を含有する印刷インキの組成、重ね刷り白インキの有無、及び積層体の構成を記す。尚、実施例5においては塩酢ビ樹脂を過剰に用い、また実施例6,7においてはレーザ発色剤レーザフレア820、トマテック42−903Aを使用した。
( Reference Examples 2 to 5 , Examples 6 and 7, Reference Examples 8 and 9 , Comparative Examples 1 and 2)
In Table 1, the composition of the printing ink containing the vinyl chloride resin used in Reference Examples 2-5, Examples 6, 7, Reference Examples 8, 9, and Comparative Examples 1 and 2, presence or absence of overprinting white ink And the structure of the laminate. In Example 5, vinyl chloride resin was used in excess, and in Examples 6 and 7, laser color former Laser Flare 820 and Tomatech 42-903A were used.
なお、表1において、以下のようである。 In Table 1, it is as follows.
・白色顔料:チタニックスJR805(テイカ株式会社製)
・黄色顔料:LIONOL YELLOW1823G(東洋インキ製造株式会社製)
・塩酢ビ樹脂:SOLBIN C、A(日信化学工業、MEK30%溶液に調整)
・ウレタン樹脂:合成例1による
・アクリル樹脂:合成例2による
・白色インキ:製造例1による
・レーザフレア820(メルク社製)
・トマテック42−903A(東罐マテリアル・テクノロジー社製)
・透明プラスチックフイルム(1): OPP パイレンP2161(東洋紡績社 製、膜厚20μm)
・基材(3):PET UX−FCD(トーセロ社製、膜厚40μ)
CPP CP GHC(トーセロ社製、膜厚30μm)
・ White pigment: Titanics JR805 (manufactured by Teika)
Yellow pigment: LIONOL YELLOW 1823G (manufactured by Toyo Ink Manufacturing Co., Ltd.)
・ Vinyl chloride resin: SOLBIN C, A (Nisshin Chemical Industry, adjusted to MEK 30% solution)
-Urethane resin: according to Synthesis Example 1-Acrylic resin: according to Synthesis Example 2-White ink: according to Production Example 1-Laser flare 820 (Merck)
・ Tomatec 42-903A (manufactured by Toago Material Technology)
-Transparent plastic film (1): OPP Pyrene P2161 (manufactured by Toyobo Co., Ltd., film thickness 20 μm)
-Substrate (3): PET UX-FCD (manufactured by Tosero Co., Ltd., film thickness 40 μ)
CPP CP GHC (manufactured by Tosero Co., Ltd., film thickness 30 μm)
(レーザ印字)
参考実施例2〜5、実施例6、7、参考実施例8、9、および比較例1、2で得られたレーザマーキング用積層体について、YVO4レーザ「キーエンス社製MD-9600」を用い、レーザによる印字を行った。印字条件は、実施例1〜9、比較例1、2共に共通で、レーザ照射は何れも透明プラスチックフイルム(1)側より行った。
1)LD% 30%
2)Q−スイッチ周波数 10kHz
3)走査速度 500mm/秒
(Laser printing)
For the laser marking laminates obtained in Reference Examples 2 to 5 , Examples 6 and 7, Reference Examples 8 and 9 , and Comparative Examples 1 and 2, a YVO4 laser “MD-9600 manufactured by Keyence Corporation” was used. Laser printing was performed. The printing conditions were common to Examples 1 to 9 and Comparative Examples 1 and 2, and laser irradiation was performed from the transparent plastic film (1) side.
1) LD% 30%
2) Q-switch frequency 10 kHz
3) Scanning speed 500mm / sec
(評価)
レーザ印字を行なった積層体について視認性試験(目視)を行い、印字濃度を評価した。試験方法について以下に説明する。
視認性:目視
印字した積層体を昼光下で、そのまま観察し、その視認性を目視で評価した。結果 を表2に示す。
◎:印字濃度が非常に濃く、視認性が非常に良い
○:印字濃度が濃く、視認性が良好。
△:印字濃度が劣るが、視認できる。
×:印字濃度が殆どない、また、視認性が殆どない。
(Evaluation)
A visibility test (visual observation) was performed on the laminate subjected to laser printing, and the printing density was evaluated. The test method will be described below.
Visibility: visual observation The printed laminated body was observed as it was under daylight, and the visibility was evaluated visually. The results are shown in Table 2.
A: The print density is very high and the visibility is very good. O: The print density is high and the visibility is good.
Δ: Print density is inferior, but visible.
X: Almost no print density and almost no visibility.
Claims (9)
塩酢ビ樹脂を含有する印刷インキが、
白色顔料もしくは黄色顔料
の少なくともいずれかを含有し、かつ、
ウレタン樹脂
を含有し、さらに
印刷インキの固形分100重量部中、塩酢ビ樹脂を、20〜90重量部
含有し、さらに、
レーザ照射で発色する発色剤
を含有することを特徴とするレーザマーキング用積層体。 A laminate for laser marking comprising a transparent plastic film (1), an ink film layer (2) formed from a printing ink containing a vinyl chloride resin, and a substrate (3) ,
Printing ink containing vinyl chloride resin is
White or yellow pigment
And containing at least one of
Urethane resin
Contains
20 to 90 parts by weight of vinyl chloride resin in 100 parts by weight of solid content of printing ink
Contains, and
Color former that develops color by laser irradiation
A laminate for laser marking, comprising:
Laser marked laminate characterized in that it is obtained by the method according to any one claims 5 to 8.
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JP2014000734A (en) * | 2012-06-19 | 2014-01-09 | Toyo Ink Sc Holdings Co Ltd | Internal printing method by laser marking |
JP6186707B2 (en) * | 2012-11-30 | 2017-08-30 | 大日本印刷株式会社 | Multi-layer film for laser printing |
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JP6545559B2 (en) * | 2015-07-31 | 2019-07-17 | サカタインクス株式会社 | PRINTING INK COMPOSITION FOR LAMINATE AND EASILY TREABLE LAMINATE |
JP2016137719A (en) * | 2016-02-18 | 2016-08-04 | キユーピー株式会社 | Method for laser-marking on packaging film, packaging film, package body, and packaged food using package body as container |
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