JP2011126142A - Laminate for laser marking - Google Patents
Laminate for laser marking Download PDFInfo
- Publication number
- JP2011126142A JP2011126142A JP2009287043A JP2009287043A JP2011126142A JP 2011126142 A JP2011126142 A JP 2011126142A JP 2009287043 A JP2009287043 A JP 2009287043A JP 2009287043 A JP2009287043 A JP 2009287043A JP 2011126142 A JP2011126142 A JP 2011126142A
- Authority
- JP
- Japan
- Prior art keywords
- laser
- laminate
- printing
- oxide
- laser 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.)
- Granted
Links
- 238000010330 laser marking Methods 0.000 title claims abstract description 34
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 17
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002985 plastic film Substances 0.000 claims abstract description 16
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 50
- 238000004040 coloring Methods 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
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- 239000011241 protective layer Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 238000010304 firing Methods 0.000 abstract description 6
- 239000000976 ink Substances 0.000 description 39
- 239000010408 film Substances 0.000 description 27
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- -1 polypropylene Polymers 0.000 description 13
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- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
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- 239000002904 solvent Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 206010020751 Hypersensitivity Diseases 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
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- 230000000996 additive effect Effects 0.000 description 4
- 208000026935 allergic disease Diseases 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920006257 Heat-shrinkable film Polymers 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 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
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 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
- 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
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 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
- 235000009508 confectionery Nutrition 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 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
- 238000007645 offset printing Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000002245 particle Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
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- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、レーザ照射により発色するレーザマーキング用積層体に関する。 The present invention relates to a laminate for laser marking that develops color by laser irradiation.
ＰＬ法（製造物責任法）が施工され、包装体、ラベル等には多種の印字が必要になっている。偽造、欠陥等の事故を防ぐセキュリティーの為、あるいはトレーサビリティの観点から、表示の重要性が高まっている。
その分野は、医薬品のみならず、電子機器や電子部品の他、食品類や日用品、包装品に至るまでの多種多様な製品の包装、ラベル、キャップの他、ガラス瓶、金属缶、プラスチック容器にもおよび、その製品、用途に見合った印字が求められている。
The PL Act (Product Liability Act) has been implemented, and various types of printing are required for packaging, labels, and the like. The importance of display is increasing for security to prevent accidents such as forgery and defects, or from the viewpoint of traceability.
Its fields include not only pharmaceutical products but also electronic devices and electronic parts, as well as packaging of various products ranging from foods, daily necessities, and packages, labels, caps, glass bottles, metal cans, and plastic containers. In addition, there is a demand for printing suitable for the product and application.
かかる表示は、具体的にはその型式や規格、製造年月日、賞味期限、会社ロゴマーク、産地表示、肥培管理表示、遺伝子組み替え表示、添加物表示、アレルギーに関する表示、栄養表示、成分表示、包装に関する表示であり、法で定められた情報の他、消費者が望む情報付加、生産者、販売者の商品戦略を反映した内容であり、それぞれの製品、使用状況に応じた印字が必要になっている。 Such indications are specifically the model and standard, date of manufacture, expiration date, company logo, production area indication, fertilizer management indication, genetic recombination indication, additive indication, allergy indication, nutrition indication, ingredient indication, This is a label on the packaging that reflects the information added by the consumer, the information that the consumer wants, and the product strategy of the producer and seller, and it is necessary to print according to each product and usage. It has become.
従来、包装資材、ラベル、キャップ、フイルム、容器等への印刷は、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、賞味期限、製造年月日、ロット番号の日時や機械で変化する可変印字は、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、刻印印刷法等で行われている。 Conventionally, printing on packaging materials, labels, caps, films, containers, and the like has been performed by plate systems such as gravure printing, flexographic printing, offset printing, and silk screen printing. Further, the best-before date, the date of manufacture, the date and time of the lot number, and variable printing that changes with the machine are performed by a stamp printing method, an ink jet printing method, a thermal transfer ribbon method, a stamp printing method, and the like.
可変文字の他、産地表示、肥培管理表示、栄養表示、成分表示などを行う場合、可変印字ではないにしても、小さなロットになるのは避けられない。市場ニーズ、商品戦略を反映するためには少量多品種になるが、それを有版方式で行うことは、高価な版を多数用意することになり、版コストの他、版の管理など極めて高コストで煩雑な作業となる。 In addition to variable characters, when performing production area display, fertilizer management display, nutrition display, component display, etc., it is inevitable that the lot will be small even if it is not variable printing. In order to reflect market needs and product strategies, it becomes a small quantity and a wide variety, but if you do it with a plate method, you will have to prepare a lot of expensive plates, and in addition to the plate cost, the management of the plate is extremely high Costly and cumbersome work.
本発明は、表面保護層、レーザ発色層を有するレーザマーキング用積層体についてである。該積層体のレーザ発色層は特定構造のレーザ発色剤を必須成分とし、ラベル、カード、シール、包装体に使用でき、レーザ照射により印字が可能となる。 The present invention relates to a laminate for laser marking having a surface protective layer and a laser coloring layer. The laser color-developing layer of the laminate comprises a laser colorant having a specific structure as an essential component, and can be used for labels, cards, seals, and packages, and can be printed by laser irradiation.
レーザマーキングによる積層体への印字は、一般的にはレーザ照射によるレーザ発色層の炭化、分解、気化により起こる。実際に製品名、製造者名、製造年月日、ロット番号、規格、製造年月日、賞味期限、会社ロゴマーク、産地表示、肥培管理表示、遺伝子組み替え表示、添加物表示、アレルギーに関する表示、栄養表示、成分表示等を印字した場合、表刷り構成においてはフイルム、紙基材の表面保護層がないため特にインキ層表面の膨れ、剥がれ発生しやすい。このような膨れ、剥がれは製品としての外観、見栄えを損なうばかりか、実際に使用される形態、例えば袋、箱、ラベルでの耐油性、耐水性、耐摩耗性等を著しく低下させる問題があった。
また、レーザ照射における条件を弱くすれば、表面の膨れ、剥がれは低減できるものの印字濃度が低下し、目的とする表示の視認性が低下する。また、包装体、ラベル等は、用途によっては耐水性を求められることがあるが、発色剤自体の耐水性が弱い場合が多く、印字後の濃度が低下したり、場合によっては消えたりするという問題があり、印字濃度と耐水性をともに満足するものが求められていた。
Printing on a laminate by laser marking is generally caused by carbonization, decomposition, and vaporization of a laser coloring layer by laser irradiation. Actual product name, manufacturer name, date of manufacture, lot number, standard, date of manufacture, expiration date, company logo, production area display, fertilizer management display, genetic recombination display, additive display, allergy display, When a nutrition label, a component label, or the like is printed, the surface of the ink layer is particularly prone to swelling and peeling because there is no film or surface protective layer on the paper substrate. Such swelling and peeling not only impair the appearance and appearance of the product, but also have the problem of significantly reducing the oil resistance, water resistance, wear resistance, etc. in the form actually used, such as bags, boxes, and labels. It was.
Further, if the conditions for laser irradiation are weakened, the swelling and peeling of the surface can be reduced, but the print density is lowered and the visibility of the intended display is lowered. In addition, the packaging body, label, etc. may be required to have water resistance depending on the application, but the color developing agent itself is often weak in water resistance, and the density after printing is lowered or disappears in some cases. There was a problem, and there was a demand for a printer that satisfies both the print density and water resistance.
そこで、本発明は表面保護層、レーザ発色層を有するレーザマーキング積層体において印字濃度、耐水性に優れ、製品名、製造者名、製造年月日、ロット番号、規格、製造年月日、賞味期限、会社ロゴマーク、産地表示、肥培管理表示、遺伝子組み替え表示、添加物表示、アレルギーに関する表示、栄養表示、成分表示等の印字が可能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 is excellent in printing density and water resistance in a laser marking laminate having a surface protective layer and a laser coloring layer, product name, manufacturer name, date of manufacture, lot number, standard, date of manufacture, taste. It is an object of the present invention to provide a laminate for laser marking capable of printing a deadline, a company logo, a production area display, a cultivation management display, a gene recombination display, an additive display, an allergy display, a nutrition display, a component display, and the like.
即ち、本発明は、基材上にレーザ発色層と透明プラスチックフイルムの表面保護層とを有するレーザマーキング用積層体において、レーザ発色層が酸化ビスマスと酸化ネオジムを焼成することで得られるレーザ発色剤を含有し、該酸化ビスマスと該酸化ネオジムの比率が９８．0：２．０〜９９．９：０．１であ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。
また、レーザ発色層が更に着色顔料を含有することを特徴とする前記レーザマーキング用積層体に関する。
更に、レーザ発色剤と着色顔料の比率が３０：７０〜１：９９である前記レーザマーキング用積層体に関する。
更に、レーザ発色層がポリウレタン樹脂、もしくは塩化ビニル／酢酸ビニル共重合体から選ばれる１種類以上の樹脂を含有していること前のレーザマーキング用積層体に関する。
更に、レーザマーキング用積層体の基材がプラスチックフイルムである前記レーザマーキング用積層体に関する。
更に、前記のレーザマーキング用積層体を用いた包装体に関する。
That is, the present invention relates to a laser coloring agent obtained by firing bismuth oxide and neodymium oxide in a laser marking laminate having a laser coloring layer and a surface protective layer of a transparent plastic film on a substrate. And a ratio of the bismuth oxide and the neodymium oxide is 98.0: 2.0 to 99.9: 0.1.
Further, the present invention relates to the laser marking laminate, wherein the laser coloring layer further contains a color pigment.
Furthermore, it is related with the said laminated body for laser marking whose ratio of a laser color former and a coloring pigment is 30: 70-1: 99.
Furthermore, the present invention relates to a laminate for laser marking before the laser coloring layer contains one or more kinds of resins selected from polyurethane resins or vinyl chloride / vinyl acetate copolymers.
Furthermore, the present invention relates to the laser marking laminate, wherein the base material of the laser marking laminate is a plastic film.
Furthermore, it is related with the package using the said laminated body for laser marking.
本態様のレーザマーキング用積層体は、基材上にレーザ発色層、表面保護層を有し、当該レーザ発色層は、酸化ビスマスと酸化ネオジムを焼成することで得られるレーザ発色剤を含有しているため、印字濃度が非常に高く、また耐水性に優れている。また、基材にフイルム、紙、金属箔等を用いる積層体にすると、ラベル、カード、もしくは包装体等として使用することが可能となり、表面の膨れ、剥がれがなくコントラストが鮮明な文字、図形、情報を有すコード等を記録でき、商品、製品の製造管理、流通管理、販売において管理、広告、宣伝機能を十分に発揮することができる。 The laminate for laser marking of this embodiment has a laser coloring layer and a surface protective layer on a substrate, and the laser coloring layer contains a laser coloring agent obtained by firing bismuth oxide and neodymium oxide. Therefore, the print density is very high and the water resistance is excellent. In addition, when a laminate using film, paper, metal foil, etc. is used as a base material, it can be used as a label, card, packaging, etc., and there is no blistering or peeling of the surface. A code having information can be recorded, and management, advertisement, and promotion functions can be sufficiently exhibited in product, product manufacturing management, distribution management, and sales.
本発明をなすレーザマーキング用積層体は、基材上にレーザ発色層、透明プラスチックフイルムの表面保護層を形成することで得られる。レーザ発色層は特定構造のレーザ発色剤を含有するインキ、もしくは塗料を印刷、塗工することで形成される。
本態様に用いられる基材としては、プラスチックフイルム、紙、金属箔、ガラス、木材等が挙げられる。特に、プラスチックフイルム、紙、金属箔が好ましい。更に好ましくは、プラスチックフイルムである。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、ポリエチレンテレフタレート、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。
プラスチックフイルムとして熱収縮フイルムを使用することもできる。熱収縮性フイルムとしては、ポリエステル系、スチレン系等がある。熱収縮によりフイルム基材の膨れがより低減される場合もあり、飲料用、調味料用、洗剤用等のプラスチック容器、ガラス容器の胴巻きラベルとして好適に使用できる。
また、フイルム等にアルミ、シリカ、金等を蒸着したフイルムものも使用できる。
The laminate for laser marking according to the present invention can be obtained by forming a laser color-developing layer and a transparent plastic film surface protective layer on a substrate. The laser coloring layer is formed by printing or coating an ink or paint containing a laser coloring agent having a specific structure.
Examples of the substrate used in this embodiment include plastic film, paper, metal foil, glass, and wood. In particular, plastic film, paper, and metal foil are preferable. More preferably, it is a plastic film. Plastic films such as low density polyethylene, unstretched and stretched polypropylene, polyethylene terephthalate, nylon, polystyrene, polyvinyl chloride, polycarbonate, polyvinyl alcohol film, and polyvinylidene chloride coated polypropylene, polyester, nylon, cellophane, etc. Also mentioned.
A heat-shrinkable film can also be used as the plastic film. Examples of the heat-shrinkable film include polyester and styrene. The swelling of the film base material may be further reduced by heat shrinkage, and it can be suitably used as a plastic container for beverages, seasonings, detergents, etc., and a wind-wrap label for a glass container.
Moreover, the film which vapor-deposited aluminum, silica, gold | metal | money etc. on the film etc. can also be used.
プラスチックフイルムの厚みは特に限定されないが、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。 Although the thickness of a plastic film is not specifically limited, 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.
紙としては、アート紙、コート紙、上質紙、和紙、合成紙等が使用できる。また、剥離紙を使用し、さらに粘着剤層を設けると、本発明の積層体はラベルとしても使用できる。 As paper, art paper, coated paper, high-quality paper, Japanese paper, synthetic paper, and the like can be used. Moreover, when a release paper is used and an adhesive layer is further provided, the laminate of the present invention can also be used as a label.
アルミ箔としては、印刷に適した厚さのもの、例えば厚みが５〜１５０μｍのものが使用できる。 As the aluminum foil, one having a thickness suitable for printing, for example, one having a thickness of 5 to 150 μm can be used.
表面保護層に用いる透明プラスチックフイルムとしては、前述した基材に用いたプラスチックフイルムの内、透明であればそのまま使用できる。特にポリエチレンテレフタレート、ナイロン、延伸ポリプロピレン、ポリエチレン、無延伸ポリプロピレン等が好ましい。 The transparent plastic film used for the surface protective layer can be used as it is if it is transparent among the plastic films used for the substrate. In particular, polyethylene terephthalate, nylon, stretched polypropylene, polyethylene, unstretched polypropylene and the like are preferable.
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できることにより、消字しないマーキングが可能となる。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 aspect can be printed directly inside the laminate, thereby enabling marking that does not erase. 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.
レーザ発色層は、レーザ発色印刷インキ、塗工液より形成される。好ましくは印刷インキである。レーザ発色印刷インキは、酸化ビスマスおよび酸化ネオジムの焼成体を含有していることが必要である。本化合物は自己発色性が特に強く、また化合物近傍の樹脂なども黒化させやすいため、視認性の非常に優れた印字物が得られる。 The laser coloring layer is formed from a laser coloring printing ink and a coating liquid. Printing ink is preferable. The laser color printing ink needs to contain a sintered body of bismuth oxide and neodymium oxide. Since this compound has particularly strong self-coloring properties, and the resin in the vicinity of the compound can be easily blackened, a printed matter with excellent visibility can be obtained.
本発明に用いる酸化ビスマスと酸化ネオジムを焼成したレーザ発色剤について説明する。
酸化ビスマスと酸化ネオジムをそれぞれ所要量取り、これらを小型粉砕機（例えば協立理工社製ＳＫ−Ｍ型）で乾式混合する。その後、混合粉体を電気炉（例えば、アドバンテック東洋社製、ＫＳ−１５０３）にて７００℃で１時間焼成する。さらに、焼成紛体を乳鉢で解砕する。発色剤の粒子径は０．５〜３．０μmに調整することが好ましい。
酸化ビスマスと酸化ネオジムの比率は、９８．０：２．０〜９９．９：０．１が好ましい。酸化ビスマスがさらに多くなると発色性の特長が出にくくなり、ネオジムが多くなると発色性が劣る傾向にある。本発明に使用する発色剤は、酸化ビスマスに酸化ネオジムを微量添加し、焼成するところに特徴があり、優れた発色性が発現する。酸化ネオジムは、本来単独で使用すると印字性が劣るため、これを添加しただけでは印字性能の低下を招く。本発明においては、微量添加し、高温で焼成することにより際立った印字性能の向上が見られた。これは焼成により複合体が生成し、結晶構造の変化をもたらし印字性能が向上したものと思われる。
The laser color former obtained by firing bismuth oxide and neodymium oxide used in the present invention will be described.
The required amounts of bismuth oxide and neodymium oxide are taken, and these are dry-mixed with a small pulverizer (for example, SK-M type manufactured by Kyoritsu Riko). Thereafter, the mixed powder is fired at 700 ° C. for 1 hour in an electric furnace (for example, KS-1503 manufactured by Advantech Toyo Co., Ltd.). Further, the fired powder is crushed in a mortar. The particle diameter of the color former is preferably adjusted to 0.5 to 3.0 μm.
The ratio of bismuth oxide and neodymium oxide is preferably 98.0: 2.0 to 99.9: 0.1. When the amount of bismuth oxide is further increased, it is difficult to obtain the color development characteristics, and when the amount of neodymium is increased, the color development property tends to be inferior. The color former used in the present invention is characterized in that a trace amount of neodymium oxide is added to bismuth oxide and baked, and excellent color developability is exhibited. Since neodymium oxide originally has poor printability when used alone, the addition of this causes a reduction in printing performance. In the present invention, a remarkable improvement in printing performance was observed by adding a small amount and baking at a high temperature. This seems to have resulted in the formation of a composite by firing, which changed the crystal structure and improved the printing performance.
レーザ発色性層には酸化ビスマスおよび酸化ネオジムを焼成したレーザ発色剤を有することが必須であるが、必要に応じて無機材料は、例えば、１）金属単体、２）金属塩、３）金属水酸化物、４）金属の酸化物等から選ばれる１種以上の材料を併用することが可能である。 It is essential that the laser coloring layer has a laser coloring agent obtained by baking bismuth oxide and neodymium oxide. As necessary, inorganic materials include, for example, 1) a simple metal, 2) a metal salt, and 3) a metal water. One or more materials selected from oxides, 4) metal oxides, and the like can be used in combination.
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。
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。
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。
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）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。
1) Examples of simple metals include iron, zinc, tin, nickel, copper, silver, and gold.
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) 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) 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 Materials Technology Co., Ltd.), and the like. As the metal oxide, mica, montmorillonite, smectite, etc. having a layered structure can also be used.
レーザ発色層中で、酸化ビスマスおよび酸化ネオジムを焼成したレーザ発色剤が、レーザ発色層を形成するレーザ発色印刷インキ、もしくは塗工液の固形分１００重量部中に０．３〜５０重量部含まれていると、レーザ発色層の皮膜強度、凝集力と発色性のバランスの点で好ましい。特に好ましくは、１〜４０重量部である。
０．３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、５０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された記録材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。
In the laser coloring layer, the laser coloring agent obtained by baking bismuth oxide and neodymium oxide is contained in an amount of 0.3 to 50 parts by weight in 100 parts by weight of the laser coloring printing ink forming the laser coloring layer or the solid content of the coating liquid. It is preferable from the viewpoint of the balance between the film strength of the laser coloring layer, the cohesive strength and the coloring property. Particularly preferred is 1 to 40 parts by weight.
If it is less than 0.3 parts by weight, the color developability is inferior although there is cohesion as a film. On the other hand, when the amount exceeds 50 parts by weight, the strength and cohesive strength of the film are lowered, the bending resistance of the recording material laminated by laser irradiation is lowered, and in some cases, the layers are peeled off.
顔料は印字物のバックグランドとして鮮明性、コントラスト、視認性を向上させる機能もある。本発明に使用する酸化ビスマスおよび酸化ネオジムを焼成したレーザ発色剤においては、黄色、紅色、藍色、もしくは白色顔料等の着色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。とりわけ白色顔料として酸化チタンを使用し、レーザ発色層を成す印刷インキの着色剤の一部、もしくは全部として用いると視認性の優れた印字物が得られる。酸化チタンとしてはアナターゼ、ルチル型共に使用できる。 The pigment also has a function of improving sharpness, contrast, and visibility as a background of printed matter. The laser color former obtained by firing bismuth oxide and neodymium oxide used in the present invention has high visibility laser colorability by using a color pigment such as yellow, red, indigo, or white pigment in combination as necessary. A laminate can be obtained. In particular, when titanium oxide is used as a white pigment and used as part or all of the colorant of the printing ink forming the laser coloring layer, a printed matter with excellent visibility can be obtained. Both anatase and rutile types can be used as titanium oxide.
レーザ発色剤と着色顔料の比率は３０：７０〜１：９９が好ましい。レーザ発色剤の比率が１：９９より少ないと発色性が劣る。また、レーザ発色剤の比率が３０：７０より多いと皮膜の強度、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。更に好ましくは１５：８５〜３：９７である。 The ratio between the laser color former and the color pigment is preferably 30:70 to 1:99. When the ratio of the laser color former is less than 1:99, the color developability is inferior. On the other hand, when the ratio of the laser color former is more than 30:70, the strength and cohesive strength of the film are lowered, and the bending resistance of the laminate is lowered by laser irradiation, and in some cases, the layers are peeled off. More preferably, it is 15: 85-3: 97.
レーザ発色層を構成するバインダー樹脂として、例えば水溶性の、セルロース、メチルセルロース、メトキシセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸、カゼイン、ゼラチン、スチレン／無水マレイン酸共重合体塩、イソブチレン／無水マレイン酸共重合体塩、ポリアクリル酸エステル、ポリウレタン樹脂、アクリル／スチレン樹脂等が挙げられる。溶剤型樹脂としてはスチレン／マレイン酸、アクリル／スチレン樹脂、ポリスチレン、ポリエステル、ポリカーボネイト、エポキシ樹脂、ポリウレタン樹脂、ポリブチラール樹脂、ポリアクリル酸エステル、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル酸共重合体、ポリ酢酸ビニル、塩化ビニル／酢酸ビニル共重合体等がある。これらの樹脂は単独、または２種以上混合することで得られる。
これら樹脂の中でウレタン樹脂、若しくは塩化ビニル／酢酸ビニル共重合体等から選ばれる１種以上の樹脂を用いることが好ましい。特にウレタン樹脂はフイルムへの密着性が良く、熱的緩和性にも優れていることから積層体として好適に用いられる。また、塩化ビビル／酢酸ビニル共重合体樹脂は、レーザによる発色性が良好で、発色剤等のレーザ吸収性が乏しくても、印刷インキ皮膜層としての発色性を向上させる。
Examples of the binder resin constituting the laser coloring layer include water-soluble cellulose, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, gelatin, and styrene / maleic anhydride copolymer. Examples thereof include salts, isobutylene / maleic anhydride copolymer salts, polyacrylic acid esters, polyurethane resins, and acrylic / styrene resins. Solvent type resins include styrene / maleic acid, acrylic / styrene resin, polystyrene, polyester, polycarbonate, epoxy resin, polyurethane resin, polybutyral resin, polyacrylate ester, styrene / butadiene copolymer, styrene / butadiene / acrylic acid copolymer Polymers, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers and the like. These resins can be obtained singly or by mixing two or more.
Among these resins, it is preferable to use one or more resins selected from urethane resins or vinyl chloride / vinyl acetate copolymers. In particular, a urethane resin is preferably used as a laminate because it has good adhesion to a film and is excellent in thermal relaxation. Further, the bivir chloride / vinyl acetate copolymer resin has good color developability by laser and improves the color developability as a printing ink film layer even if the laser absorbability of a color former or the like is poor.
レーザ発色層の膜強度、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。これらイソシアネート系硬化剤は水酸基を有する樹脂と組み合わせれば、耐レーザ照射性が向上し、表面状態の優れた字物が得られる。 A curing agent can be used in combination for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance, etc. of the laser coloring layer. 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. When these isocyanate curing agents are combined with a resin having a hydroxyl group, the laser irradiation resistance is improved, and a font having an excellent surface state can be obtained.
レーザ発色層を形成するレーザ発色印刷インキ、塗工液には，印刷適性、塗工適性、皮膜物性向上のため必要に応じて顔料分散剤、消泡剤、レベリング剤、ワックス、滑剤、シランカップリング剤、防腐剤、防錆剤、可塑剤、紫外線吸収剤、難燃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。
Laser coloring printing ink and coating liquid for forming the laser coloring layer include pigment dispersants, antifoaming agents, leveling agents, waxes, lubricants, silane cups as necessary to improve printability, coating suitability and film properties. Examples thereof include a ring agent, an antiseptic, a rust inhibitor, a plasticizer, an ultraviolet absorber, and a flame retardant.
The type and amount of these additives can be appropriately selected depending on the printing method, printing substrate, and printing conditions.
レーザマーキング用積層体の生産工程について一例を説明する。
１）レーザ発色印刷インキの調整
酸化ビスマスおよび酸化ネオジムを焼成したレーザ発色剤を用いてレーザ発色印刷インキを調製する際は、レーザ発色剤を樹脂、分散剤、溶媒と共に分散することが好ましい。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。
An example of the production process of the laser marking laminate will be described.
1) Preparation of laser color printing ink When preparing a laser color printing ink using a laser colorant obtained by baking bismuth oxide and neodymium oxide, it is preferable to disperse the laser colorant together with a resin, a dispersant, and a solvent. 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.
有機溶剤としては、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、酢酸エチル、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。 As the organic solvent, known solvents used for printing can be used, and examples thereof include ethanol, isopropyl alcohol, ethyl acetate, methyl isobutyl ketone, 1-methoxy-2-propanol, toluene, xylene and the like.
レーザ発色層をなすレーザ発色性印刷インキは必要に応じて他の印刷インキ、例えば黄色インキ、紅インキ、藍インキ、白色インキにそのまま添加することで、インキ色相の異なるレーザ発色性印刷インキを得る事が可能となる。特に、レーザ発色により黒化するレーザ発色剤を含むインキを製造し、白色印刷インキに添加した場合、レーザ発色によりコントラストの高い、視認性に優れた印字物が得られる。 Laser coloring printing ink forming the laser coloring layer is added as it is to other printing inks such as yellow ink, red ink, indigo ink, and white ink as necessary to obtain laser coloring printing inks having different ink hues. Things will be possible. In particular, when an ink containing a laser color former that is blackened by laser coloring is produced and added to white printing ink, a printed matter with high contrast and excellent visibility can be obtained by laser coloring.
視認性を高めるには、前述のレーザ発色層をなすレーザ発色印刷インキの色相を変える方法の他、レーザ発色層と異なる色相を有する印刷インキをレーザ発色層に直接重ね刷りし、着色インキ層を設け、コントラストを高めることでも可能である。レーザ発色自体の色相は、通常茶色、灰色、黒色が多いことから着色インキ層に白色インキ層を用いると視認性が良好となる。 In order to improve visibility, in addition to the method of changing the hue of the laser-colored printing ink forming the laser-colored layer described above, printing ink having a hue different from that of the laser-colored layer is directly overprinted on the laser-colored layer, and the colored ink layer is formed. It is also possible to increase the contrast. Since the color of laser coloring itself is usually brown, gray, or black, visibility is improved when a white ink layer is used as a colored ink layer.
レーザ発色層及び着色インキ層を同時に白色系にすると視認性が極めて良好になる。同様な効果は、レーザ発色層を黄色系に、着色インキ層を白色系、もしくは黄色系にすることでも達成される。 When the laser color forming layer and the colored ink layer are simultaneously white, the visibility becomes extremely good. A similar effect can be achieved by making the laser coloring layer yellow, and the colored ink layer white or yellow.
このようにして、得られたレーザ発色性を有するレーザマーキング用積層体において、熱融着性を有するフイルム（シーラントフイルム）を使用することにより公知の方法で包装体を作ることができる。例えば積層体の構成として、１）ナイロン／レーザ発色層／白色インキ層／接着剤層／ポリエチレンフイルム、２）ポリエチレンテレフタレート／レーザ発色層／黄色インキ層／接着剤層／無延伸ポリプロピレン等が挙げられる。これらを公知の方法で包装体にすることがでる。 In this way, in the obtained laser marking laminate having laser colorability, a package can be made by a known method by using a film (sealant film) having heat-fusibility. For example, as the structure of the laminate, 1) nylon / laser coloring layer / white ink layer / adhesive layer / polyethylene film, 2) polyethylene terephthalate / laser coloring layer / yellow ink layer / adhesive layer / unstretched polypropylene, etc. . These can be made into a package by a known method.
包装体は、菓子、冷凍食品、調味料等を内容物とした場合、内容物の変質を抑制し、性質を保持するためにボイル、レトルト処理を施すことがある。本発明に用いたレーザ発色剤は耐水性に優れることから、ボイル、レトルト用の包装体に対しても使用することが可能である。 When the package is made of confectionery, frozen food, seasoning, or the like, the package may be subjected to boil and retort treatments to suppress deterioration of the content and retain the properties. Since the laser color former used in the present invention is excellent in water resistance, it can be used for packages for boil and retort.
レーザ印字においては積層体、若しくは包装体の一部、或いは全面に製品名、製造者名、製造年月日、ロット番号、規格、賞味期限、会社ロゴマーク、産地表示、肥培管理表示、遺伝子組み替え表示、添加物表示、アレルギーに関する表示、栄養表示、成分表示、バーコード、ＲＳＳコード、２次元コード等を印字できる。 In laser printing, the product name, manufacturer name, date of manufacture, lot number, standard, expiration date, company logo mark, production area display, manure management display, genetic recombination on the laminate or part of the package or the entire surface Display, additive display, allergy display, nutrition display, ingredient display, barcode, RSS code, two-dimensional code, etc. can be printed.
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。 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.
次いで、本態様の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。 Next, the printing method of this aspect 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 YVO 4 laser (1064 nm).
好ましくは、ＹＡＧレーザ、ＹＶＯ4レーザであり、更に好ましくは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ＹＶＯ4レーザである。 Preferably, YAG laser, a YVO 4 laser, a more preferably YVO 4 laser intensity distribution of the laser light is power distribution of a single mode.
ＹＡＧレーザ、若しくはＹＶＯ4レーザは１）ＬＤ％、２）Ｑ−スイッチ周波数、及び３）走査速度等の条件により対象物の印字品質を制御できる。例えば、キーエンス社製のＭＤ−Ｖ９６００。
ＬＤ％は、レーザ出力を表す。ＬＤ％によりレーザパワーを制御できるが、大きくし過ぎるとレーザマーキング用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、小さすぎても印字品質が低下する。
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、場合によってはレーザマーキング用積層体がダメージを受ける。また、速過ぎると、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。
レーザによる印字では、印字濃度と表面状態のバランスを取ることが重要である。レーザ発色層が内部にあるため、レーザ照射により積層体内で炭化、分解、気化が起こるとその表面に膨れ、剥がれを生じやすい。場合によっては耐溶剤性、耐水性、耐摩耗性等が低下するため、レーザ印字際しては、１）ＬＤ％、２）Ｑ−スイッチ周波数、及び３）走査速度等のバランスをとる必要がある。
With YAG laser or YVO 4 laser, the print quality of the object can be controlled by conditions such as 1) LD%, 2) Q-switch frequency, and 3) scanning speed. For example, MD-V9600 manufactured by Keyence Corporation.
LD% represents the laser output. The laser power can be controlled by LD%, but if it is too large, the laser marking 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. If it is too large or too small, the print quality will deteriorate.
The scanning speed controls the interval between printing dots, printing time, and the like. If the scanning speed is too slow, the printing dots are concentrated, and in some cases, the laser marking laminate is damaged. On the other hand, if the speed is too high, the space between the print dots becomes wide, and in some cases, the print density and the print quality are lowered.
In laser printing, it is important to balance printing density and surface condition. Since the laser coloring layer is inside, if carbonization, decomposition, or vaporization occurs in the laminated body by laser irradiation, the surface tends to swell and peel off easily. In some cases, solvent resistance, water resistance, wear resistance, etc. are reduced, so it is necessary to balance 1) LD%, 2) Q-switch frequency, 3) scanning speed, etc. during laser printing. is there.
レーザ照射は、表面保護層側から行うが、基材が透明な場合、基材側から行うことも可能である。好ましくは透明な層、基材を通して直接レーザ発色性インキ層に印字することである。 Laser irradiation is performed from the surface protective layer side, but can also be performed from the substrate side when the substrate is transparent. Preferably, printing is performed directly on the laser-colorable ink layer through a transparent layer or substrate.
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, “part” represents “part by weight” and “%” represents “% by weight”.
（合成例１）ウレタン樹脂の合成
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３−メチル−１，５―ペンタンジオールとアジピン酸からなるポリエステルジオール（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、トルエン１２４４部、メチルエチルケトン１２４４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（樹脂１）の固形分は３０％、粘度は４００ｃｐｓ（２５℃）であった。
(Synthesis Example 1) Synthesis of Urethane Resin Polyester diol composed of 3-methyl-1,5-pentanediol and adipic acid (molecular weight) in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube 1000 parts (2000, molecular weight indicates number average molecular weight measured by gel permeation chromatography) and 222 parts of isophorone diisocyanate were charged and reacted in a nitrogen atmosphere at 85 ° C. for 5 hours. Subsequently, after cooling to 40 ° C., 82 parts of isophorone diamine, 7.8 parts of di-n-butylamine, 1244 parts of toluene, 1244 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 (resin 1) thus obtained had a solid content of 30% and a viscosity of 400 cps (25 ° C.).
（合成例２）アクリル樹脂の合成
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、予め調整して置いたアクリル酸２８部、メタクリル酸メチル４３０部、アクリル酸ブチル１４０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（樹脂２）の固形分は３０％、粘度は３４０ｃｐｓ（２５℃）であった。
(Synthesis Example 2) Synthesis of acrylic resin A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube was charged with 600 parts of isopropyl alcohol, and the temperature was raised to 80 ° C. in a nitrogen atmosphere with stirring. did. Next, a mixed liquid of 28 parts of acrylic acid, 430 parts of methyl methacrylate, 140 parts of butyl acrylate and 12 parts of azobisisobutyronitrile prepared in advance was dropped 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 (resin 2) thus obtained had a solid content of 30% and a viscosity of 340 cps (25 ° C.).
（調整例１）塩化ビニル／酢酸ビニル共重合体の調整
塩酢ビ樹脂ＳＯＬＢＩＮ Ｃ ３０部（日信化学工業社製）をメチルエチルケトン７０部に溶解し、３０％溶液に調整した（樹脂３）。
(Preparation Example 1) Preparation of vinyl chloride / vinyl acetate copolymer 30 parts of vinyl acetate resin SOLBIN C (manufactured by Nissin Chemical Industry Co., Ltd.) was dissolved in 70 parts of methyl ethyl ketone to prepare a 30% solution (Resin 3).
（実施例１）
レーザ発色層をなすレーザ発色性印刷インキの調整
発色剤として酸化ビスマスと酸化ネオジムを９９．９：０．１で焼成したものを２０部、合成例１で得たウレタン樹脂（樹脂１）８０部、メチルエチルケトン３０部をペイントシェーカで練肉し、レーザ発色性印刷インキを得た。得られたインキ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、印刷用のレーザ発色性印刷インキを得た。
Example 1
Preparation of Laser Coloring Printing Ink Forming Laser Coloring Layer 20 parts of bismuth oxide and neodymium oxide fired at 99.9: 0.1 as color formers, 80 parts of urethane resin (resin 1) obtained in Synthesis Example 1 30 parts of methyl ethyl ketone was kneaded with a paint shaker to obtain a laser coloring printing ink. The obtained ink was diluted with a mixed solvent of methyl ethyl ketone, ethyl acetate and isopropyl alcohol (weight ratio 50:40:10), adjusted to 17 seconds (25 ° C.) with Zahn Carp # 3 (manufactured by Kogaisha), and used for printing. A laser coloring printing ink was obtained.
透明プラスチックフイルム基材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３０μｍのグラビア版を用いて印刷速度５０ｍ／分、乾燥温度６０℃でレーザ発色性印刷インキを印刷した。 Using a gravure plate with a plate depth of 30 μm on the treated surface side of corona discharge-treated PET (“Ester E5102” manufactured by Toyobo Co., Ltd., film thickness 12 μm) as a transparent plastic film substrate, printing speed 50 m / min, drying temperature 60 ° C. Laser coloring printing ink was printed.
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」（トーセロ社製、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／レーザ発色性印刷インキより形成されたインキ皮膜層／接着剤／ポリエチレンを有するレーザマーキング用積層体を得た。 Low-density polyethylene “TUX-FCD” (manufactured by Tosero Corp., film thickness 40 μm) was bonded to the obtained PET printed matter by dry lamination using an adhesive “TM250 / CAT-RT80” (manufactured by Toyo Morton Co., Ltd.). The obtained laminate was aged at 40 ° C. for 3 days to finally obtain a laminate for laser marking having an ink film layer / adhesive / polyethylene formed from a transparent plastic film / laser coloring printing ink.
（実施例２〜８、比較例１〜５）
表１に実験例２〜８、比較例１〜５におけるにおけるレーザ発色層をなす発色剤、発色剤／着色顔料の比率、着色顔料の種類、バインダー樹脂の種類、積層体構成について記す。レーザ発色層をなすレーザ発色性印刷インキの調整方法は実施例１と同じである。尚、比較例４においてはレーザ発色剤レーザフレア８２５を使用した。
(Examples 2-8, Comparative Examples 1-5)
Table 1 shows the color former, the ratio of color former / color pigment, the type of color pigment, the type of binder resin, and the laminate structure in the laser color development layers in Experimental Examples 2 to 8 and Comparative Examples 1 to 5. The method for adjusting the laser color forming printing ink forming the laser color developing layer is the same as in Example 1. In Comparative Example 4, a laser color former laser flare 825 was used.
・ 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）
・ウレタン樹脂：合成例１による樹脂１
・アクリル樹脂：合成例２による樹脂２
・塩化ビニル／酢酸ビニル共重合体：ＳＯＬＢＩＮ Ｃ（日信化学工業株式会社製）
調整例１による樹脂３
・発色剤１：レーザフレア８２５（メルク社製、アンチモンドープ酸化スズ被覆マイカ ）
・発色剤２：トマテック４２−９０３Ａ（東罐マテリアル・テクノロジー株式会社製、
銅モリブデン複合酸化物）
・ＰＥ：ＴＵＸ−ＦＣＤ（東セロ株式会社製、膜厚４０μｍ）
・紙：ＪＥＴスター（日本大昭和板紙株式会社製、ボール紙）
・アルミ箔：住軽アルミ箔株式会社製、膜厚１２μｍ
・Ｎｙ：ＯＮ−ＲＴ（ユニチカ株式会社製、膜厚１５μｍ）
・ White pigment: Titanics JR805 (manufactured by Teika)
Yellow pigment: LIONOL YELLOW 1823G (manufactured by Toyo Ink Manufacturing Co., Ltd.)
Urethane resin: Resin 1 from Synthesis Example 1
Acrylic resin: Resin 2 from Synthesis Example 2
-Vinyl chloride / vinyl acetate copolymer: SOLBIN C (manufactured by Nissin Chemical Industry Co., Ltd.)
Resin 3 according to Adjustment Example 1
Color former 1: Laser flare 825 (Merck, antimony-doped tin oxide-coated mica)
Color developing agent 2: Tomatec 42-903A (manufactured by Toago Material Technology Co., Ltd.,
Copper molybdenum composite oxide)
-PE: TUX-FCD (manufactured by Tosero Co., Ltd., film thickness 40 μm)
・ Paper: JET Star (made by Nippon Daishowa Paperboard Co., Ltd., cardboard)
・ Aluminum foil: Sumi Light Aluminum Foil Co., Ltd., film thickness 12μm
・ Ny: ON-RT (manufactured by Unitika Ltd., film thickness 15 μm)
実施例１〜８および比較例１〜４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」を使用してレーザによる印字を行った。印字条件は
（１） 走査速度＝５００ｍｍ／秒
（２）Ｑ−スイッチ周波数＝１０ｋＨｚ
（３）レーザパワー１０％
である。
The laser marking laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were printed with a laser using a YVO 4 laser “MD-9600 manufactured by Keyence Corporation”. Printing conditions are: (1) Scanning speed = 500mm / sec (2) Q-switch frequency = 10kHz
(3) Laser power 10%
It is.
印字内容は、「Ｌｏｔ．ＡＢＣ１２３」である。 The print content is “Lot.ABC123”.
得られた印字物について印字濃度、耐水性を評価した。
各試験方法について以下に説明する。
The printed matter obtained was evaluated for print density and water resistance.
Each test method will be described below.
印字濃度：５段階で評価した。結果を表１に示す。
◎：印字濃度が極めて高く、視認性が極めて良好。
〇：印字濃度が高く、視認性が良好。
〇△：印字濃度が十分であり、視認性が比較的良好。
△：印字濃度が不十分であり、視認性が不良。
×：印字濃度が殆どなく、視認性が極めて不良。
尚、実用レベルは〇△以上である。
Print density: evaluated in 5 stages. The results are shown in Table 1.
A: The print density is extremely high and the visibility is very good.
◯: Print density is high and visibility is good.
○ Δ: The print density is sufficient and the visibility is relatively good.
Δ: Print density is insufficient and visibility is poor.
X: There is almost no printing density and visibility is very poor.
The practical level is ◯ Δ or more.
耐水性：３段階で評価した。結果を表１に示す。
〇：印字濃度がまったく低下しない。
△：印字濃度が僅かに低下する。
×：印字濃度が著しく低下する。
尚、実用レベルは△以上である。
○: Print density does not decrease at all.
Δ: Print density slightly decreases.
X: Print density is remarkably reduced.
The practical level is Δ or more.
表１から明らかな様に、耐水性に優れ、印字濃度に優れたレーザーマーキング用積層体を提供できる。 As is clear from Table 1, it is possible to provide a laser marking laminate having excellent water resistance and excellent print density.
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