OA21199A - Security documents or articles comprising optical effect layers comprising magnetic or magnetizable pigment particles and methods for producing said optical effect layers. - Google Patents
Security documents or articles comprising optical effect layers comprising magnetic or magnetizable pigment particles and methods for producing said optical effect layers. Download PDFInfo
- Publication number
- OA21199A OA21199A OA1202300072 OA21199A OA 21199 A OA21199 A OA 21199A OA 1202300072 OA1202300072 OA 1202300072 OA 21199 A OA21199 A OA 21199A
- Authority
- OA
- OAPI
- Prior art keywords
- platelet
- magnetic
- coating layer
- pigment particles
- magnetizable pigment
- Prior art date
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 499
- 239000002245 particle Substances 0.000 title claims abstract description 383
- 239000000049 pigment Substances 0.000 title claims abstract description 333
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000003287 optical effect Effects 0.000 title claims abstract description 46
- 239000011247 coating layer Substances 0.000 claims abstract description 278
- 239000010410 layer Substances 0.000 claims abstract description 89
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 160
- 239000013598 vector Substances 0.000 claims description 68
- 239000008199 coating composition Substances 0.000 claims description 40
- 230000005855 radiation Effects 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007639 printing Methods 0.000 description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 22
- 239000011651 chromium Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 17
- 238000000576 coating method Methods 0.000 description 15
- 238000007650 screen-printing Methods 0.000 description 13
- 239000006096 absorbing agent Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- -1 hématite (FezCh) Chemical class 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 230000000007 visual effect Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000712 assembly Effects 0.000 description 5
- 238000000429 assembly Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229910001004 magnetic alloy Inorganic materials 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003098 cholesteric effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000010408 film Substances 0.000 description 4
- 238000007647 flexography Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 241000242759 Actiniaria Species 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 241000254158 Lampyridae Species 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007649 pad printing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- UQLLWWBDSUHNEB-CZUORRHYSA-N Cefaprin Chemical compound N([C@H]1[C@@H]2N(C1=O)C(=C(CS2)COC(=O)C)C(O)=O)C(=O)CSC1=CC=NC=C1 UQLLWWBDSUHNEB-CZUORRHYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002544 Olefin fiber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004775 Tyvek Substances 0.000 description 1
- 229920000690 Tyvek Polymers 0.000 description 1
- 241001147416 Ursus maritimus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229940081090 cefa Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 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
- 239000004922 lacquer Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002417 nutraceutical Substances 0.000 description 1
- 235000021436 nutraceutical agent Nutrition 0.000 description 1
- 239000004767 olefin fiber Substances 0.000 description 1
- 238000007557 optical granulometry Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000015541 sensory perception of touch Effects 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
The invention relates to the field of the protection of security documents such as for example banknotes and identity documents against counterfeit and illegal reproduction. In particular, the present invention provides security documents and decorative articles comprising one or more optical effect layers (OELs) and methods for producing said OELs, said OELs comprising magnetically oriented platelet-shaped magnetic or magnetizable pigment particles in an at least partially cured coating layer (x10) and exhibiting an eye-catching optical effect thus allowing an observer to easily authenticate said OELs upon titling at viewing/observation angles between about -45° and about +45°.
Description
SECURITY DOCUMENTS OR ARTICLES COMPRISING OPTICAL EFFECT LAYERS COMPRISING MAGNETIC OR MAGNETIZABLE PIGMENT PARTICLES AND METHODS FOR PRODUCING SAID OPTICAL EFFECT LAYERS
FIELD OF THE INVENTION
[001] The présent invention relates to the field of optical effect layers (OELs) comprising magnetically oriented magnetic or magnetizable pigment particles. In particular, the présent invention provides security documents and décorative articles comprising one or more optical effect layers (OELs) and methods for producing said OELs and the use of said OELs as anticounterfeit means on security documents or security articles as well as décorative purposes.
BACKGROUND OF THE INVENTION
[002] It is known in the art to use inks, compositions, coatings or layers containing oriented magnetic or magnetizable pigment particles, particularly also optically variable magnetic or magnetizable pigment particles, for the production of security éléments, e.g. in the field of security documents. Coatings or layers comprising oriented magnetic or magnetizable pigment particles are disclosed for example in US 2,570,856; US 3,676,273; US 3,791,864; US 5,630,877 and US 5,364,689. Coatings or layers comprising oriented magnetic color-shifting pigment particles, resulting in particularly appealing optical effects, useful for the protection of security documents, hâve been disclosed in WO 2002/090002 A2 and WO 2005/002866 Al.
[003] Security features, e.g. for security documents, can generally be classified into “covert” security features on the one hand, and “overt” security features on the other hand. The protection provided by covert security features relies on the principle that such features are diffîcult to detect, typically requiring specialized equipment and knowledge for détection, whereas “overt” security features rely on the concept of being easily détectable with the unaided human senses, e.g. such features may be visible and/or détectable via the tactile sense while still being diffîcult to produce and/or to copy. However, the effectiveness of overt security features dépends to a great extent on their easy récognition as a security feature.
[004] Magnetic or magnetizable pigment particles in printing inks or coatings allow for the production of magnetically induced images, designs and/or patterns through the application of a correspondingly structured magnetic field, inducing a local orientation of the magnetic or magnetizable pigment particles in the not yet hardened/cured (i.e. wet) coating, followed by the hardening of the coating. The resuit is a fixed and stable magnetically induced image, design or pattern. Materials and technologies for the orientation of magnetic or magnetizable pigment particles in coating compositions hâve been disclosed for example in US 2,418,479; US 2,570,856; US 3,791,864, DE 2006848-A, US 3,676,273, US 5,364,689, US 6,103,361, EP 0 406 667 Bl; US
2002/0160194; US 2004/0009308; EP 0 710 508 Al; WO 2002/09002 A2; WO 2003/000801 A2; WO 2005/002866 Al; WO 2006/061301 Al. In such a way, magnetically induced patterns which are highly résistant to counterfeit can be produced. The security element in question can only be produced by having access to both, the magnetic or magnetizable pigment particles or the corresponding ink, and the particular technology employed to print said ink and to orient said pigment in the printed ink.
[005] As described for example in WO 2015/018663 Al, it is known in the art thathigh contrast, brightness and reflectivity are essential for overt security features comprising of magnetically oriented pigments or particles.
[006] According to the magnetic orientation pattern of the magnetic or magnetizable pigment particles an optical effect layer (OEL) and to the observation direction, said OEL may display bright and dark areas. The optical properties of spécifie zones of the OEL are directly dépendent on the orientation of the magnetic or magnetizable pigment particles in the coating layer forming said OEL.
[007] EP 2 484 455 B1 discloses OELs comprising jointly visible zones of a first and second hardened coating compositions comprising pigment particles oriented to imitate a first and a second curved surfaces. As disclosed in EP 2 484 455 B1 and the prior art cited therein in [003], in particular WO 2004/007095 A2, coating compositions comprising pigment particles oriented to imitate a curved surface produce a specular reflection zone that would be seen by an observer as a bright zone moving upon tilting the substrate carrying the coating composition (i.e. upon varying the observation direction).
[008] EP 2 846 932 B1 discloses OELs with platelet-shaped magnetic or magnetizable pigment particles oriented such as to display a pattern of bright and dark areas which appear to move, or to appear and disappear when the viewing angle of the optical effect layer changes. As disclosed in [0046], based on their shape, the particles hâve their maximum reflectivity (maximum projection area) in a direction perpendicular to their extended surface, and accordingly, at orthogonal view, in the image of the OEL, the bright areas correspond to particles whose orientation approximately matches that of the surface, i.e. which hâve a low angle 0 with respect to the surface of the OEL such that the incident light is substantially reflected back in the same (orthogonal) direction.
[009] In the field of authenticating an overt security element comprising magnetically oriented platelet-shaped magnetic or magnetizable pigment particles, an observer tilts said security element so as to verify its genuineness from a normal direction (i.e. an observation direction perpendicular to the substrate surface carrying the security element) to grazing angles (i.e. observation directions substantially parallel to the substrate surface), i.e. from ± 90°. However, non-expert observers, even though they hâve been trained about the security element, typically tilt the security element in a narrower range, typically at not larger than ±45° from the normal to the substrate onto which said element is présent. Furthermore, the man in the Street may not always benefit from the best illumination conditions for the inspection/authentication of the security element.
[010] Prior art documents do not provide any information of the orientation and suitable élévation angles of magnetically oriented particles to produce OELs that exhibit a significative and observable variation (i.e. increase and decrease) of brightness upon conventional tilting by an observer in the process of authenticating said element.
[011] Therefore, a need remains for optical effect layers (OELs) and methods for producing said OELs, said OELs exhibiting an eye-catching and easily recognizable visual appearance by exhibiting highly contrasting highly reflective (bright) and non-reflective (dark) areas at suitable observation angles for the man in the Street so at to easily authenticate of said OEL.
SUMMARY OF THE INVENTION
[012] Accordingly, it is an object of the présent invention to overcome the deficiencies of the prior art.
[013] This is achieved by the provision of a security document or a décorative object comprising a substrate (x20) having a two-dimensional surface and one or more optical effect layers (OELs) on said substrate (x20), wherein said one or more optical effect layers (OELs) comprise magnetically oriented platelet-shaped magnetic or magnetizable pigment particles having a main axis X and being in an at least partially cured coating layer (xlO), wherein an orientation of the platelet-shaped pigment particles is defined by a platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, and wherein the platelet vectors of the platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an élévation angle □ □, said élévation angle □ □ being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°), so that the one or more optical effects layers (OELs) exhibit an increase of brightness to reach a maximum value of brightness and a decrease of brightness within a viewing angle from -45° to +45 ° of the substrate (x20).
[014] The one or more optical effect layers (OELs) described herein comprise mono-axially oriented platelet-shaped magnetic or magnetizable pigment particles or comprise bi-axially oriented platelet-shaped magnetic or magnetizable pigment particles
[015] Also described herein are security documents or articles described herein further comprising one or more indicia, said one or more indicia being présent between the substrate (x20) and the one or more optical effect layers (OELs).
[016] Also described herein are security documents or articles described herein, wherein the one or more optical effect layers (OELs) comprise the magnetically oriented platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (xlO) and comprise magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles in an at least partially cured second coating layer (xl 1), wherein the at least partially cured second coating layer (xl 1) is either at least partially or fully overlapping the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xl 1) is adjacent to the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xl 1) is spaced apart from the at least partially cured coating layer (xlO), wherein the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the twodimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle D‘ in the at least partially cured second coating layer (xll), the additional élévation angle □ □ ‘ being larger than 0° and smaller than 3 0° (0° < □ ' < 3 0°) or larger than 150° and smaller than 180° (150° < □' < 180°), said élévation angle □□ and additional élévation angle being different from each other and/or being not coplanar.
[017] Also described herein are methods for producing the optical effect layers (OELs) described herein and optical effect layers (OELs) obtained thereof. Also described herein are methods for producing an optical effect layer (OEL) on a substrate (x20) having a two-dimensional surface, said method comprising the steps of:
a) applying on the substrate (x20) surface a radiation curable coating composition comprising platelet-shaped magnetic or magnetizable pigment particles, said radiation curable coating composition being in a first, liquid State so as to form a coating layer (xlO);
b) exposing the coating layer (xlO) to a magnetic field of a magnetic-field generating device (x30) in one or more areas wherein the magnetic field is substantially homogeneous so as to orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the coating layer (xlO) is provided in said one or more areas wherein the magnetic field is substantially homogeneous with an angle □ □ □ formed by the coating layer (xlO) and a tangent to magnetic field lines of the magnetic field within the one or more areas wherein the magnetic field is substantially homogeneous being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°);
c) partially simultaneously with or subsequently to step b), a step of at least partially curing the coating layer (xl0) with a curing unit (x40) so as to at least partially fix the position and orientation of the platelet-shaped magnetic or magnetizable pigment parti clés in the coating layer (xlO) so as to produce an at least partially cured coating layer (xlO), wherein an orientation of the platelet-shaped pigment particles is defined by a platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, and wherein the platelet vectors of the platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an élévation angle □ □, said élévation angle □ □ being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°).
[018] The step b) of exposing the coating layer (xlO) described herein may be carried out so as to mono-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles so that the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other. Altematively, the step b) of exposing the coating layer (xlO) described herein may be carried out so as to bi-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles having the main axis X described herein and a second main axis Y, the orientation being further defined by a second platelet vector which is the vector parallel to the second main axis Y of the particle, so that the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and the second platelet vectors of said neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other.
[019] Also described herein are methods for producing optical effect layers (OELs) comprising the at least partially cured coating layer (xlO) comprising the platelet-shaped magnetic or magnetizable pigment particles and an at least partially cured second coating layer (xll) comprising second platelet-shaped magnetic or magnetizable pigment particles, wherein said at least partially cured second coating layer (xll) may be at least partially or fully on said at least partially cured coating layer (xl 0) or may be at adjacent to or spaced apart from the at least partially cured coating layer (xlO), wherein an orientation of each of the second platelet-shaped pigment particles is defined by the platelet vector which is the vector parallel to the main axis X of the second platelet-shaped pigment particles, wherein the platelet vectors of neighboring second platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, and wherein the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle □ ‘ being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), said élévation angle □ □ and additional élévation angle □ □ ‘ being different from each other and/or being not coplanar.
[020] The présent invention provides optical effect layers (OELs) comprising magnetically oriented magnetic or magnetizable pigment particles having spécifie élévation angles such as to exhibit highly contrasting highly reflective (bright) and non-reflective (dark) areas upon variation of the tilting angle by the man in the Street and under diffuse illumination conditions without requiring complicated manipulations. Therefore, the OELs described herein may be easily authenticated by the man in the Street.
BRIEF DESCRIPTION OF DRAWINGS
[021] The security documents or articles comprising the one or more optical effect layers (OELs) described herein and the methods described herein for producing said OELs on substrates (x20) are now described in more details with reference to the drawings and to particular embodiments, wherein
Fig. 1 schematically illustrâtes a front view of an OEL as seen by the man in the Street, wherein said man in the Street tilts about a tilting axis □ the OEL with an observation angles from -45° to +45° so as to easily authenticate an OEL on a substrate having a two-dimensional surface.
Fig. 2A schematically illustrâtes a platelet-shaped particle with its main axis X and its main axis Y.
Fig. 2B schematically illustrate mono-axially oriented platelet-shaped particles, wherein the platelet vectors (vectors parallel to the main axis X of the particle) of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other. Fig. 2C schematically illustrate bi-axially oriented platelet-shaped particles, wherein the platelet vectors (vectors parallel to the main axis X of the particle) of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and the second platelet vectors (vectors parallel to the main axis Y of the particle) of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other.
Fig. 3A schematically illustrâtes a cross-section of an OEL comprising magnetically oriented platelet-shaped magnetic or magnetizable pigment particles in a coating layer (310) on a substrate (320).
Fig. 3B schematically illustrâtes a cross-section (along a plane perpendicular to the tilting axis □ of the OEL) of an OEL comprising a single at least partially cured coating layer (310) comprising platelet-shaped magnetic or magnetizable pigment particles in one or more first zones (310-a) and platelet-shaped magnetic or magnetizable pigment particles in one or more second zones (310-b), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the one or more zones (310-a) hâve substantially the same élévation angle □ and substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the one or more zones (310-b) hâve substantially the same additional élévation angle said élévation angle □ and additional élévation angle □’ being different from each other and/or being not coplanar.
Fig. 3C schematically illustrâtes a cross-section of an OEL comprising an at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein and an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer (311) partially overlapping the at least partially cured coating layer (310), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (310) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same additional élévation angle said élévation angle □ and additional élévation angle □ ’ being different from each other and/or being not coplanar.
Fig. 3D schematically illustrâtes a cross-section of an OEL comprising an at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein and an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer (311) fully overlapping the at least partially cured coating layer (310), wherein ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (310) hâve substantially the same élévation angle □ and ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same additional élévation angle said élévation angle □ and additional élévation angle □’ being different from each other and/or being not coplanar.
Fig. 3E schematically illustrâtes a cross-section of an OEL comprising an at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein and an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer being adjacent to the at least partially cured coating layer (310), wherein ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (310) hâve substantially the same élévation angle □ and ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same additional élévation angle said élévation angle □ and additional élévation angle □ C’being different from each other and/or being not coplanar.
Fig. 4A1 schematically illustrâtes a cross-section of a suitable magnetic-field generating device (430) for mono-axially orienting platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of a bar dipole magnet, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A with the angle □
Fig. 4A2 schematically illustrâtes a suitable magnetic-field generating device (430) for monoaxially orienting platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of two bar dipole magnets (Ml, M2) having a same magnetic direction and an iron yoke (Y), wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic field of the bar dipole magnet (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A at the spécifie angle □ □
Fig. 4B1 schematically illustrâtes (left) a suitable magnetic-field generating device (430) and a cross-section (right) of said device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of a linear arrangement of four dipole magnets (M1-M4) that are positioned in a staggered fashion or in zigzag formation, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as dotted rectangles A and A’) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A (or altematively in area A’) with the angle □ □
Fig. 4B2 schematically illustrâtes (left) a suitable magnetic-field generating device (430) and a cross-section (right) of said device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of two dipole magnets (Ml, M2) having an opposite magnetic direction, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as dotted rectangles A and A’) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A (or altematively in said area A’) with the angle □ □.
Fig. 4B3 schematically illustrâtes (left) a suitable magnetic-field generating device (430) and a cross-section (right) of said device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of two dipole magnets (Ml, M2) having a saine magnetic direction, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A with the angle □ □.
Fig. 4B4 schematically illustrâtes (left) a suitable magnetic-field generating device (430) and a top view (right) of said device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of a Halbach array comprising five dipole magnets (M1-M5), wherein the plateletshaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted parallelepiped A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A with the angle □
Fig. 4B5 schematically illustrâtes a cross-section of a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of Halbach cylinder assembly comprising four structures, each one comprising a magnet bar (M1-M4) surrounded by a magnet-wire coil (not shown), wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A with the angle □ □.
Fig. 4B6 schematically illustrâtes (left) a suitable magnetic-field generating device (430) and a top view (right) of said device (430) for bi-axially orienting at least a part of platelet-shaped magnetic or magnetizable pigment particles in a coating layer (410) on a substrate (420), said device (430) consisting of an assembly of eight bar dipole magnets (M1-M8), said assembly comprising a first set comprising a first bar dipole magnet (M4) and two second bar dipole magnets(Ml, M6), a second set comprising a first bar dipole magnet (M5) and two second bar dipole magnets (M3; M8) and a first pair of third bar dipole magnets (M2, M7), wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (430) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (420) carrying the coating layer (410) is provided in said area A at the spécifie angle □ □.
Fig. 5A schematically illustrate an oblique view (Fig. 5A1) and a cross-section (Fig. 5A2-3) of a suitable magnetic-field-generating device (530) for bi-axially orienting platelet-shaped magnetic or magnetizable pigment particles comprised in a coating layer (510) on a substrate (520) and a curing device (540). The magnetic-field-generating device (530) comprise nine bar dipole magnets (M1-M9) with altemating North-South magnetic directions and arranged in a row, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (for illustration purpose, magnets M3-M9 hâve been shown in Fig. 5A2, magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic field of the magnetic-field generating device (530) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted parallelepiped A) and wherein the substrate (520) carrying the coating layer (510) is provided in said area A with the angle □ □. Fig 5A3 illustrâtes a process wherein the at least partially curing step with the curing device (540) is carried out partially simultaneously with the magnetic orientation step.
Fig. 6AB schematically illustrate front views of a magnetic-field-generating device (630) for mono-axially orienting platelet-shaped magnetic or magnetizable pigment particles comprised in a coating layer (610) on a substrate (620) and a curing device (640). The magnetic-field-generating device (630) comprise two bar dipole magnets (Ml, M2) and two pôle pièces (PI, P2) arranged as a rectangular assembly, wherein the platelet-shaped magnetic or magnetizable pigment particles are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic field of the magnetic-field generating device (630) in one area wherein the magnetic field is substantially homogeneous (shown as a dotted rectangle A) and wherein the substrate (620) carrying the coating layer (610) is provided in said area A with the angle □ Fig 6B1 illustrate a process wherein the at least partially curing step is carried out partially simultaneously with the magnetic orientation step and Fig. 6B2 illustrâtes a process wherein the at least partially curing step is carried out subsequently to the magnetic orientation step.
Fig. 7A show photographie images of OELs, said OELs being obtained by using the method and device shown in Fig. 5.
Fig. 7B illustrâtes curves of the brightness values of the OELs comprising bi-axially oriented pigment particles shown in Fig. 7A and having different élévation angles □, wherein the OELs hâve been printed on a transparent PET substrate disposed on a black substrate. The y-axis represents the brightness of the OEL in arbitrary units as calculated on 100 x 100 pixels areas of OEL’s pictures, the x-axis representing the observation angles Θ.
Fig. 8 show photographie images of OELs comprising bi-axially oriented pigment particles and similar to Fig. 3D, said OELs being obtained by using the method and device shown in Fig. 5.
Fig. 9A-B illustrâtes curves of brightness values of two OELs comprising mono-axially oriented pigment particles with an élévation angle □ of about 20°, wherein the OELs hâve been printed on a transparent PET substrate disposed on a black substrate (Fig. 9A) or on a white substrate (Fig. 9B). The y-axis represents the brightness of the OEL in arbitrary units as calculated on 100 x 100 pixels areas of OEL’s pictures, the x-axis representing the observation angles Θ..
Fig. 10 schematically illustrâtes an apparatus for taking the photographie images shown in Fig. 7A and 8 at different observation angles 0, the apparatus comprising an intégration sphere (IS), an illumination source (L), a caméra (C) and a movable holder (H) for the samples (S), the caméra (C) and the movable holder (H) being fixed on a plate (P), so as to vary the observation angle θ of the sample.
[022] The magnetic fïcld Unes (shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (x30) shown in the figures for illustration purpose hâve been obtained by simulation, said magnetic field simulations hâve been performed with the software Vizimag 3.19.
DETAILED DESCRIPTION
Définitions
[023] The following définitions are to be used to interpret the meaning of the ternis discussed in the description and recited in the claims.
[024] As used herein, the terni “at least one” is meant to define one or more than one, for example one or two or three.
[025] As used herein, the ternis “about” and “substantially” mean that the amount or value in question may be the spécifie value designated or some other value in its neighborhood. Generally, the ternis “about” and “substantially” denoting a certain value is intended to dénoté a range within ± 5% of the value. As one example, the phrase “about 100” dénotés a range of 100 ± 5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the invention can be obtained within a range of ±5% of the indicated value.
[026] The ternis “substantially parallel” refer to deviating not more than 2° as averaged on a coating layer surface of at least 1 mm2, or on at least about 100 particles from parallel alignment. [027] As used herein, the term “and/or” means that either ail or only one of the éléments of said group may be présent. For example, “A and/or B” shall mean “only A, or only B, or both A and B”. In the case of “only A”, the term also covers the possibility that B is absent, i.e. “only A, but not B”.
[028] The term “comprising” as used herein is intended to be non-exclusive and open-ended. Thus, for instance a coating composition comprising a compound A may include other compounds besides A. However, the term “comprising” also covers, as a particular embodiment thereof, the more restrictive meanings of “consisting essentially of’ and “consisting of’, so that for instance “a mixture comprising A, B and optionally C” may also (essentially) consist of A and B, or (essentially) consist of A, B and C.
[029] The term “optical effect layer (OEL)” as used herein dénotés a coating layer that comprises oriented magnetic or magnetizable pigment particles, wherein said magnetic or magnetizable pigment particles are oriented by a magnetic field and wherein the oriented magnetic or magnetizable pigment particles are fixed/frozen in their orientation and position (i.e. after curing) so as to form a magnetically induced image.
[030] The term coating composition refers to any composition which is capable of forming an optical effect layer (OEL) on a solid substrate and which can be applied preferably but not exclusively by a printing method. The coating composition comprises the platelet-shaped magnetic or magnetizable pigment particles described herein and the binder described herein.
[031] As used herein, the term “wet” refers to a coating layer which is not yet at least partially cured, for example a coating in which the platelet-shaped magnetic or magnetizable pigment particles are still able to change their positions and orientations under the influence of extemal forces acting upon them.
[032] The term security document refers to a document which is usually protected against counterfeit or fraud by at least one security feature. Examples of security documents include without limitation value documents and value commercial goods.
[033] The term “security feature” is used to dénoté an image, pattern or graphie element that can be used for authentication purposes.
[034] Where the présent description refers to “preferred” embodiments/features, combinations of these “preferred” embodiments/features shall also be deemed as disclosed as long as this combination of “preferred” embodiments/features is technically meaningful.
[035] The présent invention provides security documents and décorative articles comprising a substrate (x20) having a two-dimensional surface and one or more optical effect layers (OELs) on said substrate (x20), wherein said OELs are based on magnetically oriented platelet-shaped magnetic or magnetizable pigment particles, wherein the orientation of the substrate (x20) is defined by a substrate vector which is the local normal vector to the substrate (x20) perpendicular to the two-dimensional surface of the substrate (x20) at the respective position of the one or more optical effect layers (OELs).
[036] Typical examples of décorative articles include without limitation luxury goods, cosmetic packaging, automotive parts, electronic/electrical appliances, fumiture and fingemail articles. Altematively, the one or more OELs described herein may be comprised onto an auxiliary substrate such as for example a label and consequently transferred to a décorative article in a separate step.
[037] Security documents include without limitation value documents and value commercial goods. Typical example of value documents include without limitation banknotes, deeds, tickets, checks, vouchers, fiscal stamps and tax labels, agreements and the like, identity documents such as passports, identity cards, visas, driving licenses, bank cards, crédit cards, transactions cards, access documents or cards, entrance tickets, public transportation tickets, academie diploma or titles and the like, preferably banknotes, identity documents, right-conferring documents, driving licenses and crédit cards. The term “value commercial good” refers to packaging materials, in particular for cosmetic articles, nutraceutical articles, pharmaceutical articles, alcohols, tobacco articles, beverages or foodstuffs, electrical/electronic articles, fabrics or jewelry, i.e. articles that shall be protected against counterfeiting and/or illégal reproduction in order to warrant the content of the packaging like for instance genuine drugs. Examples of these packaging materials include without limitation lahels, such as authentication brand labels, tamper evidence labels and seals. It is pointed out that the disclosed substrates, security documents and décorative articles are given exclusively for exemplifying purposes, without restricting the scope of the invention. Altematively, the one or more OELs described herein may be comprised onto an auxiliary substrate such as for example a security thread, security stripe, a foil, a decal, a window or a label and consequently transferred to a security document in a separate step.
[038] The shàpe of the one or more OELs described herein may be continuous or discontinuous. According to one embodiment, the shape of the one or more OELs independently represent one or more indicia, dots and/or lines. For embodiments wherein the security documents and décorative articles comprise more than one, i.e. two, three, etc., OELs, said OELs may be adjacent or spaced apart.
[039] As mentioned herein, the eye-catching OELs described herein allows an observer to easily authenticate them upon titling between about -45° and about +45°. The eye-catching visual appearance is seen as a sharp and contrasted switch-on / switch off effect of the brightness and consists off an increase of the brightness value to reach a maximum value of brightness and then a decrease of said brightness within the viewing/obscrvation angles about -45° and about +45°, said brightness change being observable with the naked eye.
[040] As shown in Fig. 1, the man in the Street usually tilts about the tilting axis □ the OEL with an observation angles from -45° to +45°, wherein said OEL may be tilted about i) a vertical/longitudinal axis (up/down motion) or ii) about a horizontal/latitudinal axis (left/right motion). However, any other kind of tilting axes □ may be used.
[041] For embodiments wherein the security document or décorative article comprises a single OEL, the eye-catching visual appearance may be seen upon tilting about i) a vertical/longitudinal axis or ii) about a horizontal/latitudinal axis.
[042] For embodiments wherein the security document or décorative article comprises at least two OELs, the eye-catching visual appearance of both of said two OELs may be seen upon tilting about i) a vertical/longitudinal axis or ii) about a horizontal/latitudinal axis; altematively, the eyecatching visual appearance of one of said two OELs may be seen upon tilting about a vertical/longitudinal axis while, the eye-catching visual appearance of the other of said two OELs may be seen upon tilting about a horizontal/latitudinal axis.
[043] The platelet-shaped magnetic or magnetizable pigment particles are comprised in the radiation curable coating composition described herein as well as the coating layer (xlO) as well as the at least partially cured coating layer (xlO). As mentioned herein, the methods described herein comprise the step c) of at least partially curing the coating layer (xlO) to a second State, where the platelet-shaped magnetic or magnetizable pigment particles are fixed in their current positions and orientations and can no longer move nor rotate within said layer. As used herein, by “at least partially curing the coating layer (xlO)”, it means that the platelet-shaped magnetic or magnetizable pigment particles are fîxed/frozen in their adopted positions and orientations and cannot move and rotate anymore (also referred in the art as “pinning” of the particles).
[044] As mentioned therein, the one or more optical effect layers (OELs) described herein comprise the magnetically oriented platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer. Preferably, the platelet-shaped magnetic or magnetizable pigment particles described herein are présent in an amount from about 5 wt-% to about 40 wt-%, more preferably about 10 wt-% to about 30 wt-%, the weight percentages being based on the total weight of at least partially cured coating layer. Preferably, the platelet-shaped magnetic or magnetizable pigment particles described herein are présent in an amount from about 5 wt-% to about 40 wt-%, more preferably about 10 wt-% to about 30 wt-%, the weight percentages being based on the total weight of the radiation curable coating layer described herein.
[045] Platelet-shaped magnetic or magnetizable pigment particles described herein are defined as having, due to their non-spherical shape, non-isotropic reflectivity with respect to an incident electromagnetic radiation for which the cured binder material is at least partially transparent. As used herein, the term “non-isotropic reflectivity” dénotés that the proportion of incident radiation from a first angle that is reflected by a particle into a certain (viewing/observation) direction (a second angle) is a function of the orientation of the particles, i.e. that a change of the orientation of the particle with respect to the first angle can lead to a different magnitude of the reflection to the viewing/observation direction. Preferably, the platelet-shaped magnetic or magnetizable pigment particles described herein hâve a non-isotropic reflectivity with respect to incident electromagnetic radiation in some parts or in the complété wavelength range of from about 200 to about 2500 nm, more preferably from about 400 to about 700 nm, such that a change of the particle’s orientation results in a change of reflection by that particle into a certain direction. As known by the man skilled in the art, the magnetic or magnetizable pigment particles described herein are different from conventional pigments, in that said conventional pigment particles exhibit the same color and reflectivity, independent of the particle orientation, whereas the magnetic or magnetizable pigment particles described herein exhibit either a reflection or a color, or both, that dépend on the particle orientation. In contrast to needle-shaped pigment particles which can be considered as one-dimensional particles, platelet-shaped pigment particles hâve an X-axis and a Y-axis defining a plane of prédominant extension of the particles (Fig. 2A). In other words and as shown in Fig. 2A, platelet-shaped pigment particles may be considered to be two-dimensional particles due to the large aspect ratio of their dimensions, wherein the dimensions X and Y are substantially larger than dimension Z. Platelet-shaped pigment particles are also referred in the art as oblate particles or flakes. Such pigment particles may be described with a main axis X corresponding to the longest dimension Crossing the pigment particle and a second main axis Y perpendicular to X which also lies within said pigment particles.
[046] The orientation of the platelet-shaped magnetic or magnetizable pigment particles is defmed by a platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other (see Fig. 2B), and wherein the platelet vectors of the plateletshaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by the élévation angle □ □ described herein. The élévation angle □ □ described herein is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°). More preferably, the élévation angle □ □ is in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
[047] OELs comprising platelet-shaped magnetic or magnetizable pigment particles with an élévation angle of 0° are not distinguishable and could be imitated with non-magnetic pigments typically disperesed in solvent based inks, wehrein upon solvent évaporation the pigments are forced to adopt élévation angle of 0°.
[048] As shown for example in Fig. 3A, the platelet-shaped magnetic or magnetizable pigment particles are oriented as described above with the élévation angle □ □ described herein. In other words, the élévation angle is formed by the main axis X of the platelet-shaped magnetic or magnetizable pigment particles and the two-dimensional surface of the substrate (x20) and, wherein said élévation angle □ □, when measured (for example with a conoscopic scatterometer or with a microscope such as described hereafter) in a cross-section of the optical effect layer (OEL) and measured in a counterclockwise direction, is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°). More preferably, the élévation angle □□ is in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
[049] For embodiments wherein the platelet-shaped magnetic or magnetizable pigment particles are mono-axially oriented as shown for example in Fig. 2B, the orientation of the platelet-shaped pigment particles is defined by the platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other; i.e. only the main axes X of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other (in other words, neighboring platelet-shaped magnetic or magnetizable pigment particles hâve a substantially same élévation angle □ □ □.
[050] For embodiments wherein the platelet-shaped magnetic or magnetizable pigment particles are bi-axially oriented as shown for example in Fig. 2C, the orientation of the platelet-shaped pigment particles is defined by the platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and is further defined by a second platelet vector which is the vector parallel to the second axis Y of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and the second platelet vectors of said neighboring plateletshaped magnetic or magnetizable pigment particles are substantially parallel to each other. For embodiments wherein the platelet-shaped magnetic or magnetizable pigment particles are biaxially oriented shown for example in Fig. 2C, the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and not only the main axes X of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other (in other words, neighboring platelet-shaped magnetic or magnetizable pigment particles hâve a substantially same élévation angle □ □ □ but also the main axes Y of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other. For embodiments wherein the platelet-shaped magnetic or magnetizable pigment particles are bi-axially oriented as shown for example in Fig. 2C, the platelet-shaped magnetic or magnetizable particles are substantially parallel to each other.
[051 ] Suitable examples of platelet-shaped magnetic or magnetizable pigment particles described herein include without limitation pigment particles comprising a magnetic métal selected from the group consisting of cobalt (Co), iron (Fe), and nickel (Ni); a magnetic alloy of iron, manganèse, cobalt, nickel or a mixture of two or more thereof; a magnetic oxide of chromium, manganèse, cobalt, iron, nickel or a mixture of two or more thereof; or a mixture of two or more thereof. The term “magnetic” in reference to the metals, alloys and oxides is directed to ferromagnetic or ferrimagnetic metals, alloys and oxides. Magnetic oxides of chromium, manganèse, cobalt, iron, nickel or a mixture of two or more thereof may be pure or mixed oxides. Examples of magnetic oxides include without limitation iron oxides such as hématite (FezCh), magnetite (FesCh), chromium dioxide (CrCh), magnetic ferrites (MFeiCU), magnetic spinels (MR2O4), magnetic hexaferrites (MFei2Oi9), magnetic orthoferrites (RFeCh), magnetic gamets MjR.2(AO4)3, wherein M stands for two-valent métal, R stands for three-valent métal, and A stands for four-valent métal.
[052] Examples of platelet-shaped, magnetic or magnetizable pigment particles described herein include without limitation pigment particles comprising a magnetic layer M made from one or more of a magnetic métal such as cobalt (Co), iron (Fe), or nickel (Ni); and a magnetic alloy of iron, cobalt or nickel, wherein said magnetic or magnetizable pigment particles may be multilayered structures comprising one or more additional layers. Preferably, the one or more additional layers are layers A independently made from one or more selected from the group consisting of métal fluorides such as magnésium fluoride (MgF2), Silicon oxide (SiO), Silicon dioxide (S1O2), titanium oxide (T1O2), and aluminum oxide (AI2O3), more preferably Silicon dioxide (S1O2); or layers B independently made from one or more selected from the group consisting of metals and métal alloys, preferably selected from the group consisting of reflective metals and reflective métal alloys, and more preferably selected from the group consisting of aluminum (Al), chromium (Cr), and nickel (Ni), and still more preferably aluminum (Al); or a combination of one or more layers A such as those described hereabove and one or more layers B such as those described hereabove. Typical examples of the platelet-shaped magnetic or magnetizable pigment particles being multilayered structures described hereabove include without limitation A/M multilayer structures, A/M/A multilayer structures, A/M/B multilayer structures, A/B/M/A multilayer structures, A/B/M/B multilayer structures, A/B/M/B/A/multilayer structures, B/M multilayer structures, B/M/B multilayer structures, B/A/M7A multilayer structures, B/A/M/B multilayer structures, B/A/M/B/A/multilayer structures, wherein the layers A, the magnetic layers M and the layers B are chosen from those described hereabove.
[053] According to one embodiment, at least a part of the preferred platelet-shaped, magnetic or magnetizable particles is constituted by platelet-shaped optically variable magnetic or magnetizable pigment particles. Optically variable pigments refer to pigment exhibiting a change of lightness or a combination of a change of lightness and a change of hue. According to one embodiment, at least a part of the platelet-shaped, magnetic or magnetizable particles is constituted by particles exhibiting a metallic color, more preferably a silver color or a gold color.
[054] In addition to the overt security provided by the colorshifting property of the optically variable magnetic or magnetizable pigment particles, which allows easily detecting, recognizing and/or discriminating an article or security document carrying an ink, coating composition, or coating layer comprising the optically variable magnetic or magnetizable pigment particles described herein from their possible counterfeits using the unaided human senses, the optical properties of the optically variable magnetic or magnetizable pigment particles may also be used as a machine readable tool for the récognition of the OEL. Thus, the optical properties of the optically variable magnetic or magnetizable pigment particles may simultaneously be used as a covert or semi-covert security feature in an authentication process wherein the optical (e.g.
spectral) properties of the pigment particles are analyzed and thus increase the counterfeiting résistance.
[055] The use of platelet-shaped, optically variable magnetic or magnetizable pigment particles in an OEL enhances the significance of said OEL as a security feature in security document applications, because such materials are reserved to the security document printing industry and are not commercially available to the public.
[056] Preferably, the platelet-shaped, magnetic or magnetizable pigment particles are selected from the group consisting of magnetic thin-film interférence pigment particles, magnetic cholesteric liquid crystal pigment particles, interférence coated pigment particles comprising a magnetic material and mixtures of two or more thereof.
[057] Magnetic thin film interférence pigment particles are known to those skilled in the art and are disclosed e.g. in US 4,838,648; WO 2002/073250 A2; EP 0 686 675 Bl; WO 2003/000801 A2; US 6,838,166; WO 2007/131833 Al; EP 2 402 401 Bl; WO 2019/103937 Al; WO 2020/006286 Al and in the documents cited therein. Preferably, the magnetic thin film interférence pigment particles comprise pigment particles having a five-layer Fabry-Perot multilayer structure and/or pigment particles having a six-layer Fabry-Perot multilayer structure and/or pigment particles having a seven-layer Fabry-Perot multilayer structure and/or pigment particles having a multilayer structure combining one or more multilayer Fabry-Perot structures.
[058] Preferred five-layer Fabry-Perot multilayer structures consist of absorber/dielectric/reflector/dielectric/absofber multilayer structures wherein the reflector and/or the absorber is also a magnetic layer, preferably the reflector and/or the absorber is a magnetic layer comprising nickel, iron and/or cobalt, and/or a magnetic alloy comprising nickel, iron and/or cobalt and/or a magnetic oxide comprising nickel (Ni), iron (Fe) and/or cobalt (Co).
[059] Preferred six-layer Fabry-Perot multilayer structures consist of absorber/dielectric/reflector/magnetic/dielectric/absorber multilayer structures.
[060] Preferred seven-layer Fabry Perot multilayer structures consist of absorber/dielectric/reflector/magnetic/reflector/dielectric/absorber multilayer structures such as disclosed in US 4,838,648.
[061] Preferred pigment particles having a multilayer structure combining one or more FabryPerot structures are those described in WO 2019/103937 Al and consist of combinations ofat least two Fabry-Perot structures, said two Fabry-Perot structures independently comprising a reflector layer, a dielectric layer and an absorber layer, wherein the reflector and/or the absorber layer can each independently comprise one or more magnetic materials and/or wherein a magnetic layer is sandwich between the two structures. WO 2020/006/286 Al and EP 3 587 500 Al disclose further preferred pigment particles having a multilayer structure.
[062] Preferably, the reflector layers described herein are independently made from one or more selected from the group consisting of metals and métal alloys, preferably selected from the group consisting of reflective metals and reflective métal alloys, more preferably selected from the group consisting of aluminum (Al), silver (Ag), copper (Cu), gold (Au), platinum (Pt), tin (Sn), titanium (Ti), palladium (Pd), rhodium (Rh), niobium (Nb), chromium (Cr), nickel (Ni), and alloys thereof, even more preferably selected from the group consisting of aluminum (Al), chromium (Cr), nickel (Ni) and alloys thereof, and still more preferably aluminum (Al). Preferably, the dielectric layers are independently made from one or more selected from the group consisting of métal fluorides such as magnésium fluoride (MgFz), aluminum fluoride (AIF3), cérium fluoride (CeFa), lanthanum fluoride (LaFa), sodium aluminum fluorides (e.g. NasAlFô), neodymium fluoride (NdFs), samarium fluoride (SmFs), barium fluoride (BaFa), calcium fluoride (CaF?), lithium fluoride (LiF), and métal oxides such as Silicon oxide (SiO), silicium dioxide (S1O2), titanium oxide (T1O2), aluminum oxide (AI2O3), more preferably selected from the group consisting of magnésium fluoride (MgF2) and Silicon dioxide (S1O2) and still more preferably magnésium fluoride (MgF?). Preferably, the absorber layers are independently made from one or more selected from the group consisting of aluminum (Al), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), titanium (Ti), vanadium (V), iron (Fe) tin (Sn), tungsten (W), molybdenum (Mo), rhodium (Rh), Niobium (Nb), chromium (Cr), nickel (Ni), métal oxides thereof, métal sulfides thereof, métal carbides thereof, and métal alloys thereof, more preferably selected from the group consisting of chromium (Cr), nickel (Ni), métal oxides thereof, and métal alloys thereof, and still more preferably selected from the group consisting of chromium (Cr), nickel (Ni), and métal alloys thereof. Preferably, the magnetic layer comprises nickel (Ni), iron (Fe) and/or cobalt (Co); and/or a magnetic alloy comprising nickel (Ni), iron (Fe) and/or cobalt (Co); and/or a magnetic oxide comprising nickel (Ni), iron (Fe) and/or cobalt (Co). When magnetic thin film interférence pigment particles comprising a seven-layer Fabry-Perot structure are preferred, it is particularly preferred that the magnetic thin film interférence pigment particles comprise a seven-layer Fabry-Perot absorber/dielectric/reflector/magnetic/reflector/dielectric/absorber multilayer structure consisting of a Cr/MgF2/Al/Ni/Al/MgF2/Cr multilayer structure.
[063] The magnetic thin film interférence pigment particles described herein may be multilayer pigment particles being considered as safe for human health and the environment and being based for example on fïve-layer Fabry-Perot multilayer structures, six-layer Fabry-Perot multilayer structures and seven-layer Fabry-Perot multilayer structures, wherein said pigment particles include one or more magnetic layers comprising a magnetic alloy having a substantially nickelfree composition including about 40 wt-% to about 90 wt-% iron, about 10 wt-% to about 50 wt-% chromium and about 0 wt-% to about 30 wt-% aluminum. Typical examples of multilayer pigment particles being considered as safe for human health and the environment can be found in EP 2 402 401 B1 whose content is hereby incorporated by reference in its entirety.
[064] Suitable magnetic cholesteric liquid crystal pigment particles exhibiting optically variable characteristics include without limitation magnetic monolayered cholesteric liquid crystal pigment particles and magnetic multilayered cholesteric liquid crystal pigment particles. Such pigment particles are disclosed for example in WO 2006/063926 Al, US 6,582,781 and US 6,531,221. WO 2006/063926 Al discloses monolayers and pigment particles obtained therefrom with high brilliance and colorshifting properties with additional particular properties such as magnetizability. The disclosed monolayers and pigment particles, which are obtained therefrom by comminuting said monolayers, include a three-dimensionally crosslinked cholesteric liquid crystal mixture and magnetic nanoparticles. US 6,582,781 and US 6,410,130 disclose platelet-shaped cholesteric multilayer pigment particles which comprise the sequence A’/B/A2, wherein A1 and A2 may be identical or different and each comprises at least one cholesteric layer, and B is an interlayer absofbing ail or some of the light transmitted by the layers A1 and A2 and imparting magnetic properties to said interlayer. US 6,531,221 discloses platelet-shaped cholesteric multilayer pigment particles which comprise the sequence A/B and optionally C, wherein A and C are absofbing layers comprising pigment particles imparting magnetic properties, and B is a cholesteric layer.
[065] Suitable interférence coated pigment particles comprising one or more magnetic materials include without limitation structures consisting of a substrate selected from the group consisting of a core coated with one or more layers, wherein at least one of the core or the one or more layers hâve magnetic properties. For example, suitable interférence coated pigment particles comprise a core made of a magnetic material such as those described hereabove, said core being coated with one or more layers made of one or more métal oxides, or they hâve a structure consisting of a core made of synthetic or naturel micas, layered silicates (e.g. talc, kaolin and sericite), glasses (e.g. borosilicates), Silicon dioxides (SiCh), aluminum oxides (AI2O3), titanium oxides (T1O2), graphites and mixtures of two or more thereof. Furthermore, one or more additional layers such as coloring layers maÿ be présent.
[066] The platelet-shaped, magnetic or magnetizable pigment particles described herein preferably hâve a size d50 between about 2 Dm and about 50 Dm (as measured by direct optical granulometry).
[067] The platelet-shaped magnetic or magnetizable pigment particles described herein may be surface treated so as to protect them against any détérioration that may occur in the coating composition and coating layer and/or to facilitate their incorporation in said coating composition and coating layer; typically corrosion inhibitor materials and/or wetting agents may be used.
[068] According to one embodiment shown for example in Fig. 3A, the OELs described herein comprise a single at least partially cured coating layer (310) with magnetically oriented plateletshaped magnetic or magnetizable pigment particles incorporated therein, wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles hâve substantially the same élévation angle □ □ □
[069] According to one embodiment shown for example in Fig. 3B-E, the OELs described herein comprise two zones comprising the platelet-shaped magnetic or magnetizable pigment particles, wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the one zone hâve substantially the same élévation angle □ and substantially ail the platelet-shaped magnetic or magnetizable pigment particles in another zone hâve substantially the same additional élévation angle □ wherein the élévation angle □ □ is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably, in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°) and wherein the additional élévation angle □’ is larger than 0° and smaller than 30° (0° < □’ < 30°) or larger than 150° and smaller than 180° (150° < □ ’ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □’ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □’ < 175°), more preferably, in the range from about 5° to about 25° (5° < □’ < 25°) or from about 155° to about 175° (155° < □’ < 175°), said élévation angle □□ and additional élévation angle QD4 being different from each other (preferably they differ of at least 10°) and/or being not coplanar.
[070] According to one embodiment for OELs comprising platelet-shaped magnetic or magnetizable pigment particles having the élévation angle □ Qand the additional élévation angle □ being different, the additional élévation angle □’ has the following value: □’ = 180 - □, such as for example, should □ be 20°, then □ ’ is 160° (in other words, the magnetic orientation patterns of the two zones are substantially symmetric).
[071] According to one embodiment shown for example in Fig. 3B, the OELs described herein comprise a single at least partially cured coating layer (310) comprising the platelet-shaped magnetic or magnetizable pigment particles in one or more first zones (310-a) and the plateletshaped magnetic or magnetizable pigment particles in one or more second zones (310-b), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the one or more first zones (310-a) hâve substantially the same élévation angle □ and substantially ail the plateletshaped magnetic or magnetizable pigment particles in the one or more second zones (310-b) hâve substantially the same additional élévation angle □ ’, wherein the élévation angle □ □ is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ <
180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably, in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°) and wherein the additional élévation angle □’ is larger than 0° and smaller than 30° (0° < □’ < 30°) or larger than 150° and smaller than 180° (150° < □’ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □’ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □’ < 175°), more preferably, in the range from about 5° to about 25° (5° < □’ < 25°) or from about 155° to about 175° (155° < □’ < 175°), said élévation angle □□ and additional élévation angle □ □ ‘ being different from each other (preferably they differ of at least 10°) and/or being not coplanar.
[072] According to one embodiment shown for example in Fig. 3C-E, the OELs described herein comprise the at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein, wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles hâve substantially the same élévation angle DDand further comprise an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, wherein the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle D‘, the additional élévation angle DD4 being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), said élévation angle □ □ and additional élévation angle □ being different from each other. The at least partially cured second coating layer (xll) is either at least partially or fully overlapping the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xl 1) is adjacent to the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xll) is spaced apart from the at least partially cured coating layer (xlO).
[073] According to one embodiment shown for example in Fig. 3C, the OELs described herein comprise two at least partially cured coating layers (310 and 311). The OELs comprise i) the at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein as described herein and ii) an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer (311) partially overlapping the at least partially cured coating layer (310), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (310) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same additional élévation angle wherein the élévation angle □ □ is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°) and wherein the additional élévation angle □’ is larger than 0° and smaller than 30° (0° < □’ < 30°) or larger than 150° and smaller than 180° (150° < □’ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ ’ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □’ < 175°), more preferably in the range from about 5° to about 25° (5° < □’ < 25°) or from about 155° to about 175° (155° < □’ < 175°), said élévation angle □ □ and additional élévation angle □ □ ‘ being different from each other (preferably they differ of at least 10°) and/or being not coplanar.
[074] According to one embodiment shown for example in Fig. 3D the OELs described herein comprise two at least partially cured coating layers (310 and 311). The OELs comprise i) an at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein as described herein and ii) an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer (311) fully overlapping the at least partially cured coating layer (310), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (310) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same élévation angle wherein the élévation angle □ □ is larger than 0° and smaller than 30° (0°< □ <30°) or larger than 150° and smaller than 180° (150°< O < 180°),preferably larger than or equal toabout5° and smaller than30°(5°< □ <30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°) and wherein the additional élévation angle □’ is larger than 0° and smaller than 30° (0° < □ ’ < 30°) or larger than 150° and smaller than 180° (150° < □’ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □’ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □’ < 175°). more preferably in the range from about 5° to about 25° (5° < □’ < 25°) or from about 155° to about 175° (155° < □’ < 175°), said élévation angle □□ and additional élévation angle being different from each other (preferably they differ of at least 10°) and/or being not coplanar.
[075] According to one embodiment shown for example in Fig. 3E, the OELs described herein comprise two at least partially cured coating layers (310 and 311). The OELs comprise i) an at least partially cured coating layer (310) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein as described herein and ii) an at least partially cured second coating layer (311) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer being adjacent to (Fig. 3E) or spaced apart from (not shown) the at least partially cured coating layer (310), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer(310) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (311) hâve substantially the same additional élévation angle wherein the élévation angle □ □ is larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°) and wherein the élévation angle □’ is larger than 0° and smaller than 30° (0° < □’ < 30°) or larger than 150° and smaller than 180° (150° < □’ < 180°), preferably larger than or equal to about 5° and smallerthan30° (5° < □’ <30°) or largerthan 150° andsmallerthan or equal to about 175° (150° < □’ < 175°), more in the range fromabout 5° to about25° (5° < □’ < 25°) or from about 155° to about 175° (155° < □’ < 175°), said élévation angle □ □ and additional élévation angle □ □* being different from each other (preferably they differ of at least 10°) and/or being not coplanar.
[076] The substrate (x20) described herein is preferably selected from the group consisting of papers or other fibrous materials (including woven and non-woven fibrous materials), such as cellulose, paper-containing materials, glasses, metals, ceramics, plastics and polymers, metallized plastics or polymers, composite materials and mixtures or combinations of two or more thereof. Typical _paper, paper-like or other fibrous materials are made from a variety of fibers including without limitation abaca, cotton, linen, wood pulp, and blends thereof. As is well known to those skilled in the art, cotton and cotton/linen blends are preferred for banknotes, while wood pulp is commonly used in non-banknote security documents. According to another embodiment, the substrate (x20) described herein is based on plastics and polymers, metallized plastics or polymers, composite materials and mixtures or combinations of two or more thereof. Suitable examples of plastics and polymers include polyolefins such as polyethylene (PE) and polypropylene (PP) including biaxially oriented polypropylene (BOPP), polyamides, polyesters such as poly(ethylene terephthalate) (PET), poly(l,4-butylene terephthalate) (PBT), poly(ethylene 2,6-naphthoate) (PEN) and polyvinylchlorides (PVC). Spunbond olefin fibers such as those sold under the trademark Tyvek® may also be used as substrate. Typical examples of metalized plastics or polymers include the plastic or polymer materials described hereabove having a métal disposed continuously or discontinuously on their surface. Typical examples of metals include without limitation aluminum (Al), chromium (Cr), copper (Cu), gold (Au), silver (Ag), alloys thereof and combinations of two or more of the aforementioned metals. The metallization of the plastic or polymer materials described hereabove may be done by an electrodeposition process, a highvacuum coating process or by a sputtering process. Typical examples of composite materials include without limitation multilayer structures or laminates of paper and at least one plastic or polymer material such as those described hereabove as well as plastic and/or polymer fibers incorporated in a paper-like or fibrous material such as those described hereabove. Of course, the substrate can comprise further additives that are known to the skilled person, such as fillers, sizing agents, whiteners, processing aids, reinforcing or wet strengthening agents, etc. When the OELs described herein are used for décorative or cosmetic purposes including for example fingemail lacquers, said OEL may be produced on other type of substrates including nails, artificial nails or other parts of an animal or human being. The substrates (X20) described herein may be in the form of webs, sheets, thread reels, film reels, labels of the roll or label stocks.
[077] Should the one or more OELs described herein be on a security document, and with the aim of further increasing the security level and the résistance against counterfeiting and illégal reproduction of said security document, the substrate may comprise printed, coated, or lasermarked or laser-perforated indicia, watermarks, security threads, fibers, planchettes, luminescent compounds, Windows, foils, decals and combinations of two or more thereof. With the same aim of further increasing the security level and the résistance against counterfeiting and illégal reproduction of security documents, the substrate may comprise one or more marker substances or taggants and/or machine readable substances (e.g. luminescent substances, UV/visible/IR absorbing substances, magnetic substances and combinations thereof).
[078] According to one embodiment, the security documents and décorative articles comprising the substrate (x20) and the one or more OELs described herein further comprise one or more patterns, each of them independently having the shape of an indicium, wherein said one or more patterns are présent between the substrate (x20) and the one or more OELs (or in other words, the one or more OELS at least partially overlap the one or more patterns). As used herein, the tenu “indicium” and “indicia” shall mean continuous and discontinuous layer(s) consisting of distinguishing markings or signs or patterns. Preferably, the indicia described herein are selected from the group consisting of codes, symbols, alphanumeric symbols, motifs, géométrie patterns (e.g. circles, triangles and regular or irregular polygons), letters, words, numbers, logos, drawings, portraits and combinations thereof. Examples of codes include encoded marks such as an encoded alphanumeric data, a one-dimensional barcode, a two-dimensional barcode, a QR-code, datamatrix and IR-reading codes. The one or more indicia described herein may be solids indicia and/or raster indicia.
[079] According to one embodiment, the security documents and décorative articles comprising the substrate (x20) and the one or more OELs described herein further comprise one or more primer layers, wherein said one or more primer layers are présent between the substrate (x20) and the one or more OELs. This may enhance the quality of the one or more OELs described herein or promote adhesion. Examples of such primer layers may be found in WO 2010/058026 A2.
[080] With the aim of increasing the durability through soiling or Chemical résistance and cleanliness and thus the circulation lifetime of the security documents or décorative articles comprising the one or more OELs described herein, or with the aim of modifying their aesthetical appearance (e.g. optical gloss), one or more protective layers may be applied on top of the one or more OELs. When présent, the one or more protective layers are typically made of protective vamishes. Protective vamishes may be radiation curable compositions, thermal drying compositions or any combination thereof. Preferably, the one or more protective layers are radiation curable compositions, more préférable UV-Vis curable compositions. The protective layers are typically applied after the formation of the OEL.
[081] The OELs described herein may be provided directly on the substrate (x20) on which it shall remain permanently (such as for banknote applications or labels applications). Altematively, the OELs may also be provided on a temporary substrate for production purposes, from which the OELs are subsequently removed.
[082] Altematively, one or more adhesive layers may be présent on the one or more OELs or may be présent on the substrate (x20), said one or more adhesive layers being on the side of the substrate opposite to the side where the one or more OELs are provided and/or on the same side as the one or more OELs and on top of the one or more OELs. Therefore, one or more adhesive layers may be applied to the one or more OELs or to the substrate, said one or more adhesive layers being applied after the curing step has been completed. Such an object may be attached to ail kinds of documents or other articles or items without printing or other processes involving machinery and rather high effort. Altematively, the substrate described herein comprising the one or more OELs described herein may be in the form of a transfer foil, which can be applied to a document or to an article in a separate transfer step. For this purpose, the substrate is provided with a release coating, on which the one or more OELs are produced.
[083] The présent invention provides methods for producing the one or more optical effect layers (OELs) described herein on the substrates (x20) having a two-dimensional surface described herein.
[084] The methods described herein comprise the step a) of applying on the substrate (x20) surface described herein the radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles described herein, said radiation curable coating composition being in a first, liquid state which allows its application as a coating layer (xlO) and which is in a not yet at least partially cured (i.e. wet) state wherein the pigment particles can move and rotate within the layer. Since the radiation curable coating composition described herein is to be provided on the substrate (x20) surface, the radiation curable coating composition comprises at least a binder material and the magnetic or magnetizable pigment particles, wherein said composition is in a form that allows its processing on the desired printing or coating equipment. Preferably, said step a) is carried out by a printing process, preferably selected from the group consisting of screen printing, rotogravure printing, flexography printing, intaglio printing (also referred in the art as engraved copper plate printing, engraved steel die printing), pad printing and curtain coating, more preferably selected from the group consisting of screen printing, rotogravure printing, pad printing and flexography printing and still more preferably screen printing, rotogravure printing and flexography printing.
[085] The methods described herein further comprise the step b) of exposing the coating layer (xlO) to a magnetic field of a magnetic-field gencrating device (x30) so as to orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles, wherein the platelet vectors of the platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the twodimensional surface of the substrate (x20) at the positions of the particles by the élévation angle □ □, said élévation angle □ Dbeing larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably, in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
[086] The orientation of the platelet-shaped magnetic or magnetizable pigment particles and the élévation angles □ described herein are obtained by submitting the platelet-shaped magnetic or magnetizable pigment particles to the magnetic field of the magnetic-field generating device (x30) described herein in one or more areas (shown in the figures as dotted rectangles A and A’) wherein the magnetic field is substantially homogeneous (i.e. a magnetic field which has a substantially constant magnitude and direction over the entire area(s) of interest (for mono-axial orientation); or a magnetic field which is substantially confined to a plane (for bi-axial orientation), wherein the substrate (x20) carrying the coating layer (xl 0) is provided in said one or more areas with an angle □ □ formed by the coating layer (xlO) and a tangent to magnetic field lines of the magnetic field of the magnetic-field generating device (x30) within the one or more areas wherein the magnetic field is substantially homogeneous. The angle □ □ is larger than 0° and smaller than 30° (0° < □ <30°) or larger than 150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
[087] The step b) described herein is carried out to so as to mono-axially or bi-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles described herein. In contrast to a mono-axial orientation wherein magnetic or magnetizable pigment particles are orientated in such a way that only their main axis is constrained by the magnetic field (Fig. 2B), carrying out a bi-axial orientation means that the platelet-shaped magnetic or magnetizable pigment particles are made to orientate in such a way that their two main axes X and Y are constrained (Fig. 2C). That is, each platelet-shaped magnetic or magnetizable pigment particle can be considered to hâve a major axis in the plane of the pigment particle and an orthogonal minor axis in the plane of the pigment particle. The axes X and Y of the platelet-shaped magnetic or magnetizable pigment particles are each caused to orient according to the magnetic field. Effectively, this results in neighboring platelet-shaped magnetic pigment particles that are close to each other in space to be substantially parallel to each other. Put another way, a bi-axial orientation aligns the planes of the platelet-shaped magnetic or magnetizable pigment particles so that the planes of said pigment particles are oriented to be substantially parallel relative to the planes of neighboring (in ail directions) platelet-shaped magnetic or magnetizable pigment particles.
[088] According to one embodiment, the step b) is carried out to so as to mono-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles described herein. Suitable magnetic-field generating devices for mono-axially orienting the platelet-shaped magnetic or magnetizable pigment particles described herein are not limited.
[089] According to one embodiment shown in Fig. 4A1, a suitable magnetic-field generating device (430) for mono-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consiste of a bar dipole magnet. As shown in Fig. 4Al, the plateletshaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic field of the magnetic-field generating device (430) described herein in one or more areas (shown as a dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (420) carrying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[090] According to one embodiment shown in Fig. 4A2, a suitable magnetic-field generating device (430) for mono-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of an assembly comprising two bar dipole magnets (Ml, M2) having a same magnetic direction and an iron yoke (Y), wherein said magnetic-field generating device is described in US 7,047,883. As shown in Fig. 4A2, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic field of the magnetic-field generating device (430) described herein in one or more areas (shown as a dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (420) carrying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[091] According to one embodiment shown in Fig. 6A-B and used in the Examples hereafter, a suitable magnetic-field generating device (630) for mono-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of a rectangular assembly comprising two bar dipole magnets (Ml, M2) and two pôle pièces (PI, P2). The platelet-shaped magnetic or magnetizable pigment particles in the coating layer (610) on the substrate (620) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic-field generating device (630) in one or more areas (shown as an dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said area and wherein the substrate (620) carrying the coating layer (610) is provided in said one or more areas with the angle □ □ described herein.
[092] According to another embodiment, the step b) is carried out so as to bi-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles. For embodiments wherein the method described herein comprises the step of exposing the coating layer (xlO) to the magnetic field of the magnetic-field generating device (x30) described herein so as to bi-axially orient at least a part of the magnetic or magnetizable pigment particle, the coating layer (xlO) may be exposed more than one time to said magnetic-field generating device. Suitable magnetic-field generating devices for bi-axially orienting the platelet-shaped magnetic or magnetizable pigment particles described herein are not limited. As known by the man skilled in the art, bi-axial orientation of platelet-shaped magnetic or magnetizable pigment particles requires a dynamic magnetic field (i.e. time-variable/time-dependent magnetic field) that changes its direction, forcing the particles to oscillate until both main axes, X-axis and Y-axis, become aligned. In other words, bi-axial orientation requires a non-concomitant movement of the coating layer (xlO) comprising the platelet-shaped magnetic or magnetizable pigment particles with respect to the magnetic-fieldgenerating device.
[093] According to one embodiment shown in Fig. 10 of WO 2018/019594, a suitable magneticfield generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of a linear arrangement of at least four, magnets (MlM4) that are positioned in a staggered fashion or in zigzag formation. As shown in Fig. 4B1, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields of the magnetic-field generating device (430) in one or more areas (shown as dotted rectangles A, A’) wherein the magnetic field is substantially homogeneous and wherein the magnetic field fines are substantially parallel to each other in said one or more areas and wherein the substrate (420) canying the coating layer (410) is provided in said one or more areas with the angle □□ described herein. EP 2 157 141 Al discloses a similar suitable magnetic-field generating device in Fig. 5, wherein the magnetic-field generating device may be used for bi-axially orienting at least a part of the plateletshaped magnetic or magnetizable pigment particles and consists of a linear arrangement of at least three, preferably at least four, magnets that are positioned in a staggered fashion or in zigzag formation.
[094] According to one embodiment shown in Fig. 4B2 and in Fig. 8A-B of WO 2018/019594 Al, a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of two dipole magnets (Ml, M2) having an opposite magnetic direction. As shown in Fig. 4B2, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle and the South Pôle) of the magnetic fields of the magnetic-field generating device (430) in one or more areas (shown as dotted rectangles A, A’) wherein the magnetic field is substantially homogeneous and wherein the magnetic field fines are substantially parallel to each other in said one or more areas and wherein the substrate (420) canying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[095] According to one embodiment shown in Fig. 4B3 and 7A-B of WO 2018/019594 Al, a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of two dipole magnets (Ml, M2) having a same magnetic direction. As shown in Fig. 4B3, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields ofthe magnetic-field generating device (430) in one or more areas (shown as a dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (420) canying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[096] According to one embodiment shown in 4B4 and Fig. 3A-B of WO 2018/019594 Al, a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of a Halbach array comprising five dipole magnets (Ml -M5). As shown in Fig. 4B4, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields of the magnetic-field generating device (430) in one or more areas (shown as a dotted parallelepiped A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (420) carrying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[097] According to one embodiment shown in 4B5 and Fig. 12A of WO 2016/083259 Al, a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of a Halbach cylinder assembly comprising four structures, each one comprising a magnet bar (M1-M4) surrounded by a magnet-wire coil (not shown). As shown in Fig. 4B5, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field fines shown as fines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields of the magnetic-field generating device (430) in one or more areas (shown as a dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field fines are substantially parallel to each other in said one or more areas and wherein the substrate (420) canying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[098] According to one embodiment shown in 4B6 and Fig. 2A of the co-pending application EP 20176506.2, a suitable magnetic-field generating device (430) for bi-axially orienting at least a part of the platelet-shaped magnetic or magnetizable pigment particles consists of an assembly of eight bar dipole magnets (M1-M8), said assembly comprising a first set comprising a first bar dipole magnet (M4) and two second bar dipole magnets (Ml, M6), a second set comprising a first bar dipole magnet (M5) and two second bar dipole magnets (M3; M8) and a first pair of third bar dipole magnets (M2, M7). As shown in Fig. 4B6, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (410) on the substrate (420) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields of the magnetic-field generating device (430) in one or more areas (shown as a dotted rectangle A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (420) carrying the coating layer (410) is provided in said one or more areas with the angle □ □ described herein.
[099] According to one embodiment shown in Fig. 5A1-3 and used in the Examples hereafter, a suitable magnetic-field generating device (530) for bi-axially so as orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles consiste of an assembly comprising nine bar dipole magnets (M1-M9) with altemating North-South magnetic directions and arranged in a row. As shown in Fig. 5A2, the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (510) on the substrate (520) are exposed to the magnetic field (magnetic field lines shown as lines with arrows pointing from the North Pôle to the South Pôle) of the magnetic fields of the magnetic-field generating device (530) in one or more areas (shown as a dotted parallelepiped A) wherein the magnetic field is substantially homogeneous and wherein the magnetic field lines are substantially parallel to each other in said one or more areas and wherein the substrate (520) carrying the coating layer (510) is provided in said one or more areas with the angle □ □ described herein.
[0100] As known by the man skilled in the art, îf the substrate (x20) carrying the coating layer (xlO) is static or concomitantly moves with the magnetic-field generating devices (i.e. moves at the same speed as the magnetic-field generating device) shown in Fig. 4B1-4B6 and Fig. 5, the platelet-shaped magnetic or magnetizable pigment particles are mono-axially oriented upon exposure to said devices.
[0101] During the magnetic orientation described herein of the magnetic or magnetizable pigment particles, the substrate (x20) carrying the coating layer (xlO) may be disposed on a non-magnetic supporting plate (x40) which is made of one or more non-magnetic materials.
[0102] The methods described herein further comprise, partially simultaneously with or subsequently to step b), the step c) of at least partially curing the coating layer (xlO) with the curing unit (x40) described herein so as to at least partially fix the position and orientation of the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (xlO) so as to produce the at least partially cured coating layer (xlO) described herein, wherein the élévation angle □ □ described herein Dis larger than 0° and smaller than 30° (0° < □ < 30°) or larger than
150° and smaller than 180° (150° < □ < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), more preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
[0103] For embodiments, wherein the step b) is carried out to so as to bi-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles described herein, the step c) of at least partially curing the coating layer (xlO) with the curing unit (x40) described herein is preferably carried out partially simultaneously with step b).
[0104] According to one embodiment for preparing the one or more OELs such as those shown in Fig. 3B and described hereabove, i.e. said OELs comprising or consisting of the single at least partially cured coating layer (xlO) comprising the platelet-shaped magnetic or magnetizable pigment particles in one or more first zones (xlO-a) and the platelet-shaped magnetic or magnetizable pigment particles in one or more second zones (xlO-b) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein having an élévation angle □ □ in the one or more first zones (xl 0-a) and an additional élévation angle □ ‘ in the one or more second zones (xlO-b), wherein the élévation angle □ Dand additional élévation angle independently are larger than 0° and smaller than 30° (0° <□,□□'< 30°) or larger than 150° and smaller than 180° (150° <□,□□'< 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □, O □ ‘ < 30°) or larger than 150° and smaller than or equal to about 175° (150° <□,□□*< 175°), more preferably, in the range from about 5° to about 25° (5° < □, □ Q‘ <25°) or from about 155° to about 175° (155° <□,□□*< 175°), said élévation angle □ □ and élévation angle □ □ ‘ being different from each other and/or being not coplanar; the method comprises the steps of the step a) of applying on the substrate (x20) surface described herein the radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles described herein, the step b) of exposing the coating layer (xlO) to the magnetic field of the magnetic-field generating device (x30) described herein with the substrate (x20) carrying the coating layer (xlO) being provided in the one or more areas wherein the magnetic field is substantially homogeneous described herein with the angle □ □ described herein,
c) a step of selectively at least partially curing with a sélective curing unit (x50) the one or more first areas of the coating layer (xlO) to fix at least a part of the platelet-shaped magnetic or magnetizable particles in their adopted positions and orientations, such that one or more second zones (of the coating layer (xlO) remain unexposed to irradiation; said step being carried out partially simultaneously with or subsequently to step b);
d) a step of exposing the coating layer (xlO) to a second magnetic field of a second magnetic-field generating device in one or more areas wherein the second magnetic field is homogeneous so as to orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the coating layer (xlO) is provided in said one or more areas wherein the magnetic field is substantially homogeneous with an angle □ ‘,Ε formed by the coating layer (xlO) and a tangent to magnetic field fines of the second magnetic field within the one or more areas wherein the magnetic field is homogeneous, the angle □ ‘ being larger than 0° and smaller than 30° (0° < T < 30°) or larger than 150° and smaller than 180° (150° < T < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < C‘ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < IT < 175°), more preferably in the range from about 5° to about 25° (5° < T < 25°) or from about 155° to about 175° (155° < E‘ < 175°); □’ being different from □ ; and,
e) partially simultaneously with or subsequently to the step d) of exposing the coating layer (xlO) to the magnetic field of the second magnetic-field-generating device, the step c) of at least partially curing the coating layer (xlO) with the curing unit (x40) described herein.
[0105] According to one embodiment for preparing the one or more OELs such as those shown in Fig. 3C-D and described hereabove, i.e. said OELs comprising or consisting of i) an at least partially cured coating layer (xlO) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein and ii) an at least partially cured second coating layer (xl 1) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer (xll) partially or fully overlapping the at least partially cured coating layer (xlO), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (xlO) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (xll) hâve substantially the same additional élévation angle The orientation of each of the second platelet-shaped pigment particles is defined by the platelet vector described herein and the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by the additional élévation angle IT. The élévation angle □ □and additional élévation angle EUT independently are larger than 0° and smaller than 30° (0° < □, □ < 30°) or larger than 150° and smaller than 180° (150° < □, □ IT < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □, □ □ ‘ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □, □ T < 175°), more preferably, in the range from about 5° to about 25° (5° < □, DEP <25°) or from about 155° to about 175° (155° < □, < 175°), said élévation angle □□ and additional élévation angle being different from each other and/or being not coplanar, the method comprises the step of a) applying on the substrate (x20) surface described herein the radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles described herein, the step b) of exposing the coating layer (xlO) to the magnetic field of the magnetic-field generating device (x30) described herein with the substrate (x20) carrying the coating layer (xlO) being provided in the one or more areas wherein the magnetic field is substantially homogeneous described herein with the angle □ □ described herein, partially simultaneously with or subsequently to the step b), the step c) of at least partially curing the coating layer (xlO) with the curing unit (x40) described herein;
subsequently to step c), a step d) of applying either partially (Fig. 3C) or fully (Fig. 3D) on the at least partially cured coating layer (xlO) a second radiation curable coating composition comprising the second platelet-shaped magnetic or magnetizable pigment particles, said second radiation curable coating composition being in a first, liquid state so as to form a second coating layer (xl 1), wherein said second radiation curable coating composition is the same as or is different from the radiation curable coating composition of step a);
a step e) of exposing the second coating layer (xll) to a second magnetic field of a second magnetic-field generating device in one or more areas wherein the second magnetic field is homogeneous so as to orient at least a part of the second platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the second coating layer (xll) is provided in said one or more areas with an angle Ü‘,D formed by the second coating layer (xll) and a tangent to magnetic field lines of the second magnetic field within the one or more areas wherein the magnetic field is homogeneous, said angle D‘ being larger than 0° and smaller than 30° (0° < □ ' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □' < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □' < 175°), more preferably in the range from about 5° to about 25° (5° < □ ’ < 25°) or from about 155° to about 175° (155° < □' < 175°); wherein the second magnetic-field generating device is the same as or is different from the magnetic-field generating device of step b); □’ being different from □, and partially simultaneously with or subsequently to the step e) of exposing the second coating layer (xll) to thesecondmagnetic-fieldgeneratingdevice, astep f) ofatleastpartially curing thesecond coating layer (xl 1) with a curing unit (x40) so as to at least partially fix the position and orientation of second the platelet-shaped magnetic or magnetizable pigment particles in the second coating layer (xll) so as to produce the at least partially cured second coating layer (xll).
[0106] According to one embodiment for preparing the one or more OELs such as those shown in Fig. 3E and described hereabove, i.e. said OELs comprising or consisting ofi) an at least partially cured coating layer (xlO) with magnetically oriented platelet-shaped magnetic or magnetizable pigment particles incorporated therein and ii) an at least partially cured second coating layer (xl 1) with magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles incorporated therein, said at least partially cured second coating layer being adjacent to (Fig. 3E) or spaced apart (not shown) from the at least partially cured coating layer (xlO), wherein substantially ail the platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (xlO) hâve substantially the same élévation angle □ and substantially ail second platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured second coating layer (xll) hâve substantially the same additional élévation angle The orientation of each of the second platelet-shaped pigment particles is defined by the platelet vector described herein and the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by the additional élévation angle D‘. The élévation angle DDand additional élévation angle independently are larger than 0° and smaller than 30° (0° < □, □ □* < 30°) or larger than 150° and smaller than 180° (150° < □, □□* < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° <□,□□*< 30°) or larger than 150° and smaller than or equal to about 175° (150° <□,□□'< 175°), more preferably, in the range from about 5° to about25° (5°< □, 00^25°) or fromabout 155° to about 175° (155° < □, □□* < 175°), said élévation angle □□ and additional élévation angle ÜD‘ being different from each other and/or being not coplanar; the method comprises the step of a) applying on the substrate (x20) surface described herein the radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles described herein, the step b) of exposing the coating layer (xlO) to the magnetic field of the magnetic-field generating device (x30) described herein with the substrate (x20) carrying the coating layer (xlO) being provided in the one or more areas wherein the magnetic field is substantially homogeneous described herein with the angle □ □ described herein, partially simultaneously with or subsequently to the step b), the step c) of at least partially curing the coating layer (xlO) with the curing unit (x40) described herein;
subsequently to step c), a step d) of applying a second radiation curable coating composition comprising second platelet-shaped magnetic or magnetizable pigment particles, said second radiation curable coating composition being in a first, liquid State so as to form a second coating layer (xl 1), wherein said second coating layer (xl 1) is either adjacent to (Fig. 3E) or spaced apart (not shown) from the coating layer (xlO) and wherein said second radiation curable coating composition is the same as or is different from the radiation curable coating composition of step a);
a step of e) exposing the second coating layer (xl 1) to a magnetic field of a second magnetic-field generating device in one or more areas wherein the second magnetic field is homogeneous so as to orient at least a part of the second platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the second coating layer (xl 1) is provided in said one or more areas with an angle □‘,Π formed by the second coating layer (xl 1) and a tangent to the magnetic field fines of the second magnetic field within the one or more areas wherein the magnetic field is homogeneous, said angle ü‘ being larger than 0° and smaller than 30° (0° < □’ < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), preferably larger than or equal to about 5° and smaller than 30° (5° < □' < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □' < 175°), more preferably in the range from about 5° to about 25° (5° < □' < 25°) or from about 155° to about 175° (155° < □’ < 175°); wherein the second magnetic-field generating device is the same as or is different from the magnetic-field generating device of step b); □’ being different from □, and partially simultaneously with or subsequently to the step e) of exposing the second coating layer (xl 1) to the second magnetic-field generating device, a step f) of at least partially curing the second coating layer (xl 1) with a curing unit (x40) so as to at least partially fix the position and orientation of the second platelet-shaped magnetic or magnetizable pigment particles in the second coating layer (xl 1) so as to produce the at least partially cured second coating layer (xl 1 ).
[0107] Suitable curing units (x40) include equipments for UV-visible curing units comprising a high-power light-emitting-diode (LED) lamp, or an arc discharge lamp, such as a medium-pressure mercury arc (MPMA) or a metal-vapor arc lamp, as the source of the actinie radiation. The sélective curing units (x50) described herein may comprise one or more fixed or removable photomasks including one or more voids corresponding to a pattern to be formed as a part of the coating layer. The one or more sélective curing units (x50) may be addressable such as the scanning laser beam disclosed in EP 2 468 423 Al, an array of light-emitting diodes (LEDs) disclosed in WO 2017/021504 Al or an actinie radiation LED source (x41) comprising an array of individually addressable actinie radiation emitters disclosed in the co-pending patent application PCT/EP2019/087072.
[0108] According to one embodiment wherein the security documents or décorative articles comprising the substrate (x20) described herein, the one or more OELs described herein and the one or more patterns described herein between the substrate (x20) and the one or more OELs, each of them independently having the shape of an indicium, the method described herein comprises a step of applying a composition in the form of the one or more patterns having the shape of an indicium, said step occurring prior to the step a) described herein. The step of applying the composition in the form of the one or more patterns described herein may be carried out by a contactless fluid microdispensing process such as curtain coating, spray coating, aérosol jet printing, electrohydrodynamic printing and inkjet printing or may be camed out by a printing process selected from the group consisting of offset, screen printing, rotogravure printing, flexography printing, intaglio printing (also referred in the art as engraved copper plate printing, engraved Steel die printing).
[0109] Also described herein are printing apparatuses comprising one or more printing units, one or more magnetic-field-generating devices (x30) and one or more curing units (x40), the one or more printing units, the one more magnetic-field-generating devices (x30) and the one or more curing units (x40) being arranged in sequential and altemating stationaiy locations, that is so that a stationary magnetic-field-generating device (x30) is disposed after a stationaiy printing unit and before a stationary curing unit
[0110] Also described herein are printing apparatuses comprising a rotating magnetic cylinder and the one or more magnetic-field generating devices (x30) described herein, wherein said one or more magnetic-field generating devices (x30) are mounted to circumferential or axial grooves of the rotating magnetic cylinder as well as printing assemblies comprising a flatbed printing unit and one or more of the magnetic-field generating devices (x30) described herein, wherein said one or more magnetic-field generating devices (x30) are mounted to recesses of the flatbed printing unit. [0111] The rotating magnetic cylinder is meant to be used in, or in conjunction with, or being part of a printing or coating equipment, and bearing one or more of the magnetic-field generating devices (x30) described herein. In an embodiment, the rotating magnetic cylinder is part of a rotary, sheet-fed or web-fed industrial printing press that opérâtes at high printing speed in a continuons way.
[0112] The flatbed printing unit is meant to be used in, or in conjunction with, or being part of a printing or coating equipment, and bearing one or more of the magnetic-field generating devices (x30) described herein. In an embodiment, the flatbed printing unit is part of a sheet-fed industrial printing press that opérâtes in a discontinuons way.
[0113] The printing apparatuses comprising the rotating magnetic cylinder described herein or the flatbed printing unit described herein may include a substrate feeder for feeding a substrate such as those described herein having thereon the coating layer (xlO, xll) comprising the plateletshaped magnetic or magnetizable pigment particles described herein. In an embodiment of the printing apparatuses comprising a rotating magnetic cylinder described herein, the substrate is fed by the substrate feeder under the form of sheets or a web. In an embodiment of the printing apparatuses comprising a flatbed printing unit described herein, the substrate is fed under the form of sheets.
[0114] The printing apparatuses comprising the rotating magnetic cylinder described herein or the flatbed printing unit described herein may include a coating or printing unit for applying the 5 radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles described herein on the substrate (x20) described herein, In an embodiment of the printing apparatuses comprising a rotating magnetic cylinder described herein, the coating or printing unit works according to a rotary, continuous process. In an embodiment of the printing apparatuses comprising a flatbed printing unit described herein, the coating or printing unit works 10 according to a linear, discontinuons process.
[0115] The printing apparatuses comprising the rotating magnetic cylinder described herein or the flatbed printing unit described herein may include the curing unit (x40) described herein for at least partially curing the radiation curable coating composition comprising the platelet-shaped magnetic or magnetizable pigment particles that hâve been magnetically oriented by the magnetic15 field generating devices (x30) described herein, thereby fixing the orientation and position ofthe pigment particles to produce the one or more OELS described herein.
EXAMPLES
[0116] The Examples and Comparative Examples hâve been carried out by using the UV-Vis curable screen printing ink of the formula given in Table 1 and the first and second magnetic assemblies described herebelow.
Table 1
Epoxyacrylate oligomer (Allnex) | 30.1 wt-% |
Trimethylolpropane triacrylate monomer (Allnex) | 21.0 wt-% |
Tripropyleneglycol diacrylate monomer (Allnex) | 21.5 wt-% |
Genorad 16 (Rahn) | 1.1 wt-% |
Aerosil 200 (Evonik) | 1.1 wt-% |
Speedcure TPO-L (Lambson) | 2.2 wt-% |
Irgacure® 500 (IGM) | 6.4 wt-% |
Genocure® EPD (Rahn) | 2.2 wt-% |
BYK® 371 (BYK) | 2.2 wt-% |
Tego Foamex N (Evônik) | 2.2 wt-% |
magnetic pigment particles (*) | 10.0 wt-% |
(*) 5-layer platelet-shaped magnetic pigment particles exhibiting a metallic silver color having a flake shape of diameter dso about 12 pm and thickness about 1 pm, obtained from VIAVI Solutions, Santa Rosa, CA.
[0117] Examples according to the présent invention E1-E8 exhibited an eye-catching visual appearance upon tilting about a horizontal/latitudinal axis, wherein eye-catching visual appearance is seen as a sharp and contrasted switch-on / switch off effect of the brightness and consists offan increase of the brightness value to reach a maximum value of brightness and then a decrease of said brightness within the viewing/observation angles about -45° and about +45°,
Magnetic-field generating device for bi-axial orientation (Fig. 5)
[0118] A magnetic assembly (530) was used to bi-axially orient the pigment particles. The magnetic assembly (530) comprised nine bar dipole magnets (M1-M9).
[0119] Each oftheninebar dipolemagnets (M1-M9) had the following dimensions: 100 mm (Ll) x 10 mm (L2) x 10 mm (L3). The magnetic field generating device (530) was embedded in a nonmagnetic holder made of polyoxymethylene (POM) (not shown) having the following dimensions: 250 mm x 150 mm x 12 mm. The nine bar dipole magnets (M1-M9) were made of NdFeB N40.
[0120] The nine bar dipole magnets (M1-M9) were disposed in a row at a distance (dl) of about 10 mm from each other, the top surface of the nine bar dipole magnets (M1-M9) being flush. The magnetic axis of each of the nine bar dipole magnets (M1-M9) was substantially parallel to the thickness (L3) of said magnets, the magnetic direction of two neighboring magnets (M1-M9) pointing in opposite direction (altemating magnetization).
[0121] As shown in Fig. 5A1-A2, the magnetic field was substantially homogeneous and the magnetic field lines were substantially coplanar in the area A.
Magnetic-fïeld-generating device for mono-axial orientation (Fig. 6)
[0122] A magnetic field generating device (630) was used to mono-axially orient the pigment particles. The magnetic field generating device (630) comprised two bar dipole magnets (Ml, M2) and two pôle pièces (PI, P2).
[0123] Each of the two bar dipole magnets (Ml, M2) had the following dimensions: 40 mm (Ll) x 40 mm (L2) x 10 mm (L3). The two bar dipolemagnets (Ml, M2) were made of NdFeB N42.
[0124] The two bar dipole magnets (Ml, M2) were at a distance (dl) of about 40 mm from each other. The magnetic axis of each of the two bar dipole magnets (Ml, M2) was substantially parallel to the length (Ll) of said magnets, the magnetic direction of said two bar dipole magnets (Ml, M2) pointing in the same direction.
[0125] Each of the two pôle pièces (PI, P2) had the following dimensions: 60 mm (L4) x 40 mm (L5) x 3 mm (L6). The two pôle pièces (PI, P2) were made of iron (ARMCO®).
[0126] The two bar dipole magnets (Ml, M2) and the two pôle pièces (PI, P2) were disposed such as to form a rectangular cuboid with a centered rectangular cuboid void, said void consisting of the area A wherein the magnetic field was substantially homogeneous and wherein the magnetic field lines were substantially parallel to each other, such that the distance (d2) between the two pôle pièces (PI, P2) was about 40 mm, i.e. the distance (d2) between the two pôle pièces (PI, P2) was the length (Ll) of the two bar dipole magnets (Ml, M2).
E1-E5 and C1-C3 (Fig. 3A, Fig. 5, Fig. 7)
[0127] For each sample, the UV-Vis curable screen printing ink of Table 1 was applied onto on a piece of PET (BG71 Colour Laser Printer & Copier OHP Film from Folex 100 micrometers thick, 45 mm x 30 mm) (520) so as to form a coating layer (40 mm x 25 mm) (510), wherein said application step was carried out with a laboratory screen printing device using a 90T screen so as to form a coating layer (510) having a thickness of about 20 gm.
[0128] While the coating layer (510) was still in a wet and not yet at least partially cured State, the substrate (520) was placed on top of the center of a supporting plate (300 mm x 40 mm x 1 mm) made of high density polyethylene (HDPE). The supporting plate carrying the substrate (520) and the coating layer (510) were moved at a speed of about 10 cm/sec beside the magnetic-field generating device (530) (as illustrated in Fig. 5) at a distance (d5) of about 20 mm between the magnetic-field-generating device (530) surface facing the substrate (520) and the nearest edge of the coating layer (510), and aheight between said nearest coating layer (510) edge and the bottom surface of the magnetic magnetic-field generating device (530) being half the length (½ Ll) of the bar dipole magnets (M1-M9). The supporting plate carrying the substrate (520) and the coating layer (510) was concomitantly moved while adopting an angle □, formed by the coating layer (510) and a tangent to the magnetic field lines of the magnetic field of the magnetic-fieldgenerating device (530) within the area A wherein the magnetic field was homogeneous, said angle □ ühaving a value of about 1° (El), 5° (E2), 10° (E3), 20° (E4), 25° (E5), 30° (Cl), 40° (C2) and 50° (C3).
[0129] The coating layers (510) were independently at least partially cured by a curing unit (540) (UV LED larnp (FireFly 395 nm, 4W/cm2, from Phoseon) disposed above the substrate path at a distance (d4) of about 15 mm for the center of the length (Ll) of the bar dipole magnet (M1-M9), beside the space between the eighth and ninth dipole magnets (M8 and M9) and beside the ninth bar dipole magnet (M9) at a distance (d3) of about 10 mm, as illustrated in Fig. 5A1-3.
E6 (Fig. 3D, Fig. 5, Fig. 8)
[0130] The UV-Vis curable screen printing ink of Table 1 was applied onto on a piece of PET (BG71 Colour Laser Printer & Copier OHP Film from Folex 100 micrometers thick, 45 mm x 30 mm) (520) so as to form a first coating layer (510) having the shape of “A” (6 mm) (510), wherein said application step was carried out with a laboratory screen printing device using a 90T screen so as to form a coating layer (510) having a thickness of about 20 pm.
[0131] While the coating layer (510) was still in a wet and not yet at least partially cured State, the substrate (520) was placed on top of the center of a supporting plate (300 mm x 40 mm x 1 mm) made of high density polyethylene (HDPE). The supporting plate carrying the substrate (520) and the coating layer (510) was moved at a speed of about 10 cm/sec beside the magnetic-field generating device (530) (as illustrated in Fig. 5) at a distance (d5) of about 20 mm between the magnetic-field-generating device (530) surface facing the substrate (520) and the nearest edge of the coating layer (510), and a height between said nearest coating layer (510) edge and the bottom surface of the magnetic magnetic-field generating device (530) being half the length (½ Ll) ofthe bar dipole magnets (M1-M9). The supporting plate carrying the substrate (520) and the coating layer (510) were concomitantly moved while adopting an angle □, formed by the coating layer (510) and a tangent to the magnetic field lines of the magnetic field of the magnetic-fieldgenerating device (530) within the area A wherein the magnetic field was homogeneous, having a value of about 20°.
[0132] The first coating layer (510) was at least partially cured by the curing unit (540) under the same conditions/position positions as for E1-E5 and C1-C3.
[0133] For each sample, the UV-Vis curable screen printing ink of Table 1 was applied on top of the already applied coating layer (510) so as to form a second coating layer (511) having the shape of “T’ (6 xnm), wherein said application step was carried ont with a laboratory screen printing device using a 90T screen so as to form a coating layer (511) having a thickness of about 20 pm. [0134] While the second coating layer (511) was still in a wet and not yet at least partially cured State, the substrate (520) was exposed to the magnetic field of the magnetic-field-generating device (530) under the same conditions as for the first coating layer (510) except that the angle D‘ was about 160°.
[0135] The second coating layer (511) was at least partially cured by the curing unit (540) under the same conditions/position positions as for E1-E5 and C1-C3.
E7-E8 (Fig. 3A, Fig. 6, Fig. 9)
[0136] The UV-Vis curable screen printing ink of Table 1 was applied onto on a piece of PET (BG71 Colour Laser Printer & Copier OHP Film from Folex 100 micrometers thick, 45 mm x 30 mm) (620) so as to form a coating layer (40 mm x 25 mm) (610), wherein said application step was carried out with a laboratory screen printing device using a 90T screen so as to form a coating layer (610) having a thickness of about 20 pm.
[0137] While the coating layer (610) was still in a wet and not yet at least partially cured State, the substrate (620) was placed on top of the center of a supporting plate (60 mm x 40 mm x 1 mm) made of high density polyethylene (HDPE).
[0138] The supporting plate carrying the substrate (620) and the coating layer (610) were disposed in the center of the void of the magnetic assembly (630) as illustrated in Fig. 6 while adopting angle □, formed by the coating layer (610) and a tangent to magnetic field lines of the magneticfield-generating device (630) within the area A wherein the magnetic field was homogeneous, having a value of about 20°.
[0139] For sample E7, after about 1 second, the coating layer (610) was at least partially cured by a curing unit (640) (UV LED lamp (FireFly 395 nm, 4W/cm2, from Phoseon) as illustrated in Fig. 6B1.
[0140] For sample E8, subsequently to the exposure to the magnetic field, the supporting plate carrying the substrate (620) and the coating layer (610) were moved at a distance (di) of about 1 cm away from the magnetic assembly (630), the coating layer (610) was cured upon exposure during about 0.5 second to a UV-LED-lamp (640) from Phoseon (Type FireFlex 50 x 75 mm, 395 nm, 8W/cm2), as illustrated in Fig. 6B2.
Corrélation between the angles □ during the orientation step and the élévation angles □ of the pigment particles in the coating layer (xlO)
[0141] The corrélation between the angles □ during the method described hereabove and the élévation angles □ was assessed by measuring said élévation angles □ by using the conoscopic scatterometer measurements according to the method disclosed in WO 2019/038371 Al and hy measuring the élévation angles of a sélection of fïve adjacent pigment particles on a SEM picture (ZEISS EVO HD 15, using standard method of sample préparation by embedding into an epoxy matrix (Technicol 9461) with the following dimensions: 10 mm x 10 mm x30 mm) a cross-section of the coating layer (xlO). Results are provided in Table 2.
Table 2
Angle □ | Expected élévation angle □ | Elévation angle □ measured by a conoscopic scatterometer | Elévation angle □ as measured on SEM pictures | |
El | 1° | 1° | NA1 | NA2 |
E2 | 5° | 5° | NA1 | NA2 |
E3 | 10° | 10° | 11° | 10° |
E4 | 20° | 20° | 20° | 19° |
E5 | 25° | 25° | NA1 | NA1 |
Cl | 30° | 30° | 29° | NA3 |
C2 | 40° | 40° | NA3 | NA1 |
1 not measured 2 the élévation angle was too small to be measured with sufficient accuracy with SEM images 3 the élévation angle is too big to be measured by conoscopic scatterometer (total field of view is limited to 40° and the scatterometer does not allow to use 100% of the field)
[0142] The conoscopic scatterometer measurements hâve been performed by using a conoscopic scatterometer as described in WO 2019/038371 Al, Fig. 4A (obtainedfiom Eckhartd Optics LLC, 5430 Jefferson Ct, White Bear Lake, MN 55110; http://eckop.com). The élévation angles □ were measured on a coating layer surface of about 1 mm2, i.e. the reported values were averaged on about one thousand particles
[0143] SEM measurements hâve been performed by using a SEM microscope (ZEISS EVO HD15, magnification x500) on a microtome slice of the samples (slice plane perpendicular to the substrate surface and the coating layer thickness, and perpendicular to the tilting axis, as illustrated in Fig. 3). The substrates carrying the coating layer were first independently embedded in an epoxy resin (Technicol 9461) that was left to dry for 24 hours at room température before cutting and polishing the microtome slice to produce samples with the following dimensions: 10 mm x 10 mm x 30 mm. The reported values were averaged on five particles.
[0144] As illustrated in Table 2, there was an excellent corrélation between the angles □ with the measured élévation angles □.
Brightness at different observation angles Θ
[0145] The samples were disposed and fixed with a scotch tape on a paper substrate (respectively black or white). The assemblies carrying the coating layer (xlO, xl 1), the PET substrate (x20) and the paper substrate were independently disposed on a tilting holder in an intégration sphere (internai diameter 1m from Dongguan Yaoke Instrument) as illustrated in Fig. 10. The assemblies were illuminated with an illumination source (light bulb (30W, at 100% power) disposed at a distance of about 100 cm from the PET substrate surface.
[0146] A caméra (Nikon D800, lens Nikkor 105/2.8 ED, shutter speed 1/200 sec, aperture f/36, ISO 6400) was disposed on an imaginary line between the assemblies and the illumination source, at a distance of about 50 cm from the PET substrate. The images were acquired at 3680x2456 pixels (TIFF).
[0147] The holder supporting the assembly was rotated so that it was observed at observation angles Θ = 50°, 40°, 30°, 20°, 10°, 0°, -5°, -10°, -15°, -20°, -25°, -30°, -35°, -40°, -45°, -50°, -55°, -60°, -65° and -70° (0 < 0° corresponding to the assembly top edge being near the caméra; 0ü> 0° corresponding to the assembly bottom edge being near the caméra) as illustrated in Fig. 1.
[0148] The so-obtained pictures of E1-E5 and C1-C3 at different observation angles are shown in Fig. 7A and the so-obtained pictures of E6 at different observation angles are shown in Fig. 8.
[0149] The brightness of E1-E5, E7-E8 and C1-C3 were assessed using Adobe Photoshop® and by calculating the brightness average of a 100 pixels x 100 pixels area of each individual assembly comprising the coating layer (xlO, xll), the PET substrate (x20) and the paper substrate. Fig. 7B illustrâtes a graph obtained by reporting the brightness of E1-E5 and C1-C3 and Fig. 9 illustrate graphs obtained by reporting the brightness of E7-E8 at different observation angles 0 varying from —50° to +70° (x-axis : observation angles 0 [in degrees, °J; y-axis : brightness (arbitrary units)). The brightness curves are asymmetric as a resuit of the slightly less illuminated régions of the sphere due to the presence of the plate (P).
[0150] As shown in Fig. 7A-B, the optical effects layers of E1-E5 (0° < □ < 30°, in particular 5° < □ <30°, 5° < □ < 25°) exhibited an eye-catching effect and an easily observable increase of the brightness to reach a maximum value of brightness and then a decrease of said brightness value within the viewing/observation angles about -45° and about +45°.
[0151] El (1°) exhibited a maximum brightness at an observation angle Θ of about -10°; E2 (5°) exhibited a maximum brightness at an observation angle θ of about -15°; E3 (10°) exhibited a maximum value of brightness at an observation angle θ of about -25°; E4 exhibited a maximum value of brightness at an observation angle θ of about -35°; and E5 exhibited a maximum value of brightness at an observation angle θ of about -40°.
[0152] As shown in Fig. 8, the first coating layer (510 in Fig. 5, 310 in Fig. 3D) of E6 having the shape of a “A” was visible at observation angles from about 0° to about +50° with a maximum value of brightness at an observation angle of about +40°, while the second/top coating layer (511, 5 in Fig, 5, 311 Fig. 3D) having the shape of a “T” was visible from -15° to about -65° with a maximum value of brightness at an observation angle of about -35°.
[0153] As shown in Fig. 9A (black substrate) and 9B (white substrate), E7-E8 exhibited an easily observable increase and decrease of the brightness with a maximum value of brightness at an observation angles Θ of about — (20°-25°) for E7 and —(10°-15°) for E8.
Claims (15)
1. A security document or a décorative article comprising a substrate (x20) having a twodimensional surface and one or more optical effect layers (OELs) on said substrate (x20), wherein said one or more optical effect layers (OELs) comprise magnetically oriented plateletshaped magnetic or magnetizable pigment particles having a main axis X and being in an at least partially cured coating layer (xlO), wherein an orientation of the platelet-shaped pigment particles is defmed by a platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, wherein the platelet vectors of the platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions ofthe particles by an élévation angle □ □, said élévation angle O □ being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°), so that the one or more optical effects layers (OELs) exhibit an increase of brightness to reach a maximum value of brightness and a decrease of brightness within a viewing angle from -45° to +45 ° of the substrate (x20).
2. The security document or article according to claim 1, wherein at least a part of the platelet- shaped magnetic or magnetizable particles is constituted by platelet-shaped optically variable magnetic or magnetizable pigment particles.
3. The security document or article according to claim 1, wherein at least a part of the platelet- shaped magnetic or magnetizable particles is constituted by platelet-shaped magnetic or magnetizable pigment particles exhibiting a metallic color, preferably a silver color or a gold color.
4. The security document or article according to any one of claims 1 to 3, wherein the platelet- shaped magnetic or magnetizable particles are substantially parallel to each other.
5. The security document or article according to any one of claims 1 to 4, further comprising one or more indicia, said one or more indicia being présent between the substrate (x20) and the one or more optical effect layers (OELs).
6. The security document or article according to any one of daims 1 to 5, wherein the one or more optical effect layers (OELs) comprise the magnetically oriented platelet-shaped magnetic or magnetizable pigment particles in the at least partially cured coating layer (xlO) and comprise magnetically oriented second platelet-shaped magnetic or magnetizable pigment particles in an at least partially cured second coating layer (xll), wherein the at least partially cured second coating layer (xl 1) is either at least partially or fully overlapping the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xll) is adjacent to the at least partially cured coating layer (xlO), or the at least partially cured second coating layer (xll) is spaced apart from the at least partially cured coating layer (xl 0), wherein the platelet vectors of the second plateletshaped magnetic or magnetizable pigment particles are angled with respect to the twodimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle Q‘ in the at least partially cured second coating layer (xl 1), the additional élévation angle DET being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), said élévation angle □ □ and additional élévation angle □ ET being different from each other and/or being not coplanar.
7. The security document or article according to any one of daims 1 to 6, wherein the said élévation angle □ □ is larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < □ < 175°), preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° <□<175°).
8. A method for producing an optical effect layer (OEL) on a substrate (x20) having a twodimensional surface, said method comprising the steps of:
a) applying on the substrate (x20) surface a radiation curable coating composition comprising platelet-shaped magnetic or magnetizable pigment particles, said radiation curable coating composition being in a first, liquid State so as to form a coating layer (xlO); b) exposing the coating layer (xlO) to a magnetic field of a magnetic-field generating device (x30) in one or more areas wherein the magnetic field is substantially homogeneous so as to orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the coating layer (xlO) is provided in said one or more areas wherein the magnetic field is substantially homogeneous with an angle □ □□ formed by the coating layer (xlO) and a tangent to magnetic field lines of the magnetic field within the one or more areas wherein the magnetic field is substantially homogeneous, being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°)
c) partially simultaneously with or subsequently to step b), a step of at least partially curing the coating layer (xlO) with a curing unit (x40) so as to at least partially fix the position and orientation of the platelet-shaped magnetic or magnetizable pigment particles in the coating layer (xlO) so as to produce an at least partially cured coating layer (xlO), wherein an orientation of the platelet-shaped pigment particles is defmed by a platelet vector which is the vector parallel to the main axis X of the particle, wherein the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, and wherein the platelet vectors of the platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an élévation angle □ said élévation angle □ □ being larger than 0° and smaller than 30° (0° < □ < 30°) or larger than 150° and smaller than 180° (150° < □ < 180°).
9. The method according to claim 8, wherein the platelet-shaped magnetic or magnetizable pigment particles hâve a second main axis Y and the orientation of the platelet-shaped pigment particles is further defmed by a second platelet vector which is the vector parallel to the second main axis Y of the particle, and wherein the step b) of exposing the coating layer (xlO) is carried out so as to bi-axially orient at least a part of the platelet-shaped magnetic or magnetizable pigment particles, so that the platelet vectors of neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other and the second platelet vectors of said neighboring platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other.
10. The method according to claim 9, wherein the step c) is carried out partially simultaneously with step b).
11. The method according to any one of daims 8 to 10, wherein the optical effect layer (OEL) comprise the at least partially cured coating layer (xlO) comprising the platelet-shaped magnetic or magnetizable pigment particles and, at least partially on said at least partially cured coating layer (xlO), an at least partially cured second coating layer (xl 1) comprising second platelet-shaped magnetic or magnetizable pigment particles, wherein an orientation of each of the second platelet-shaped pigment particles is defined by the platelet vector which is the vector parallel to the main axis X of the second platelet-shaped pigment particles, wherein the platelet vectors of neighboring second platelet-shaped magnetic or magnetizable pigment particles are substantially parallel to each other, wherein the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle □ ‘ being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □ ' < 180°), said élévation angle □□ and additional élévation angle nü‘ being different from each other and/or being not coplanar, the method fùrther comprising:
subsequently to step c), a step d) of applying at least partially or fully on the at least partially cured coating layer (xlO) a second radiation curable coating composition comprising the second platelet-shaped magnetic or magnetizable pigment particles, said second radiation curable coating composition being in a first, liquid State so as to form a second coating layer (xl 1), wherein said second radiation curable coating composition is the same as or is different from the radiation curable coating composition of step a);
a step e) of exposing the second coating layer (xl 1) to a second magnetic field of a second magnetic-field generating device in one or more areas wherein the second magnetic field is homogeneous so as to orient at least a part of the second platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the second coating layer (xl 1) is provided in said one or more areas wherein the magnetic field is substantially homogeneous with an angle formed by the second coating layer (xl 1) and a tangent to magnetic field lines of the second magnetic field within the one or more areas wherein the magnetic field is homogeneous, being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), wherein the second magnetic-field generating device is the same or is different from the magnetic-field generating device of step b), □’ being different from □; and
f) partially simultaneously with or subsequently to the step e) of exposing the second coating layer (xl 1) to the second magnetic field, a step of at least partially curing the second coating layer (xl 1) with a curing unit (x40) so as to at least partially fix the position and orientation of the second platelet-shaped magnetic or magnetizable pigment particles in the second coating layer (xl 1) so as to produce the at least partially cured second coating layer (xll).
12. The method according to any one of claims 8 to 10, wherein the optical effect layer (OEL) comprise the at least partially cured coating layer (xlO) comprising the platelet-shaped magnetic or magnetizable pigment particles and an at least partially cured second coating layer (xll) comprisingsecondplatelet-shapedmagneticormagnetizablepigmentparticles, wherein an orientation of each of the second platelet-shaped pigment particles is defined by the platelet vector which is the vector parallel to the main axis X of the second plateletshaped pigment particles, wherein the platelet vectors of neighboring second plateletshaped magnetic or magnetizable pigment particles are substantially parallel to each other, the at least partially cured second coating layer (xll) being adjacent to or spaced apart from the at least partially cured coating layer (xlO), wherein the platelet vectors of the second platelet-shaped magnetic or magnetizable pigment particles are angled with respect to the two-dimensional surface of the substrate (x20) at the positions of the particles by an additional élévation angle □ ‘ in the at least partially cured second coating layer (xll), the additional élévation angle □ ET being larger than 0° and smaller than 30° (0° < □' < 30°) or larger than 150° and smaller than 180° (150° < □' < 180°), said élévation angle □□ and additional élévation angle DD4 being different from each other and/or being not coplanar, the method further comprising:
subsequently to step c), a step d) of applying a second radiation curable coating composition comprising the second platelet-shaped magnetic or magnetizable pigment particles, said second radiation curable coating composition being in a first, liquid State so as to form a second coating layer (xll), wherein said radiation curable coating composition is the same as or is different from the radiation curable coating composition of step a) and said second coating layer (xll) is adjacent to or spaced apart from the at least partially cured coating layer (xlO);
a step e) of exposing the second coating layer (xl 1) to a second magnetic field of a second magnetic-field generating device in one or more areas wherein the magnetic field is homogeneous so as to orient at least a part of the second platelet-shaped magnetic or magnetizable pigment particles, wherein the substrate (x20) carrying the second coating layer (xl 1) is provided in said one or more areas wherein the magnetic field is substantially homogeneous with an angle □ ‘,ü formed by the second coating layer (xll) and a tangent to magnetic field fines of the second magnetic field within the one or more areas wherein the magnetic field is substantially homogeneous, being larger than 0° and smaller than 30° (0° < D‘ < 30°) or larger than 150° and smaller than 180° (150° < ü‘ < 180°), wherein the second magnetic-field generating device is the same as or is different from the magnetic52 field generating device of step b); □’ being different from □;
f) partially simultaneously with or subsequently to the step e) of exposing the second coating layer (xll) to the second magnetic field, as step of at least partially curing the second coating layer (xl 1) with a curing unit (x40) so as to at least partially fix the position and orientation of the second platelet-shaped magnetic or magnetizable pigment particles in the second coating layer (xl 1) so as to produce the at least partially cured second coating layer (xll).
13. The method according to claim 11 or 12, wherein the angle □* is larger than or equal to about 5° and smaller than 30° (5° < D‘ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < D‘ < 175°),preferably in therangefrom about 5° to about25° (5°< □ ‘ <25°) or from about 155° to about 175° (155° < □* < 175°).
14. The method according to any one of daims 8 to 13, wherein the angle □ is larger than or equal to about 5° and smaller than 30° (5° < □ < 30°) or larger than 150° and smaller than or equal to about 175° (150° < O < 175°), preferably in the range from about 5° to about 25° (5° < □ < 25°) or from about 155° to about 175° (155° < □ < 175°).
15. An optical effect layer (OEL) produced by the method recited in any one of daims 8 to 14.
Applications Claiming Priority (1)
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EP20194060.8 | 2020-09-02 |
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OA21199A true OA21199A (en) | 2024-02-29 |
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