EP1357226B1 - Substrats avec couches électriquement conductrices - Google Patents
Substrats avec couches électriquement conductrices Download PDFInfo
- Publication number
- EP1357226B1 EP1357226B1 EP03008537A EP03008537A EP1357226B1 EP 1357226 B1 EP1357226 B1 EP 1357226B1 EP 03008537 A EP03008537 A EP 03008537A EP 03008537 A EP03008537 A EP 03008537A EP 1357226 B1 EP1357226 B1 EP 1357226B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- initiator
- catalyst
- monomer
- layer
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000003999 initiator Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 11
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000013505 freshwater Substances 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 29
- 239000000049 pigment Substances 0.000 abstract description 26
- 239000002904 solvent Substances 0.000 abstract description 26
- 239000006185 dispersion Substances 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 230000005291 magnetic effect Effects 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000004815 dispersion polymer Substances 0.000 abstract description 4
- 229920000058 polyacrylate Polymers 0.000 abstract description 3
- 239000000020 Nitrocellulose Substances 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001220 nitrocellulos Polymers 0.000 abstract description 2
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 111
- 238000003860 storage Methods 0.000 description 14
- 238000007639 printing Methods 0.000 description 13
- 239000004922 lacquer Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 239000000976 ink Substances 0.000 description 7
- 239000002346 layers by function Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002318 adhesion promoter Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 toluenesulfonate anion Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MURCDOXDAHPNRQ-ZJKZPDEISA-N L-685,458 Chemical compound C([C@@H]([C@H](O)C[C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)CC=1C=CC=CC=1)NC(=O)OC(C)(C)C)C1=CC=CC=C1 MURCDOXDAHPNRQ-ZJKZPDEISA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- 229920002521 macromolecule Polymers 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004920 heat-sealing lacquer Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method 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
- 230000001681 protective effect Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/29—Securities; Bank notes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/48—Elements suited for physical verification, e.g. by irradiation
Definitions
- the invention relates to substrates with electrically conductive layers, methods and apparatus for their preparation and their use.
- conductive paints or lacquers are usually used for printing electrically conductive layers.
- electrically conductive pigments for example carbon black, graphite, silver and the like, are added to the paints or lacquers.
- the paints and varnishes provided with these pigments are clearly visible after printing, especially on transparent substrates.
- security elements for security documents which have characters that are hidden in incident light, visible in transmitted light and which are also electrically conductive, wherein the electrically conductive material over the entire surface over at least one surface of the security element is present and transparent or semitransparent at least in some areas is executed and arranged above and / or below the characters.
- the electrically conductive material is always located on the surface of the security feature.
- the transparent or semitransparent material is realized either by an indium tin oxide layer or by sputtering a metal layer, in particular an aluminum layer.
- the object of the invention is therefore to provide a method for producing security elements with invisible, preferably transparent, electrically conductive layers, which additionally have the above-mentioned desired properties.
- the invention relates to a method for the production of security elements comprising a carrier substrate are applied to the electrically conductive layers, characterized in that the monomer ethylenedioxythiophene (EDT) is applied to the carrier substrate and is polymerized in situ using the initiator Fe (III) toluenesulfonate wherein monomer and initiator are applied in a weight ratio of 1:20 to 1: 100 and the monomer is applied with subsequent application of the initiator and / or catalyst or already mixed with the initiator and / or catalyst, wherein an electrically conductive layer of Polyethylenedioxythiophene (PEDT) which is stabilized by the non-polymer bound toluenesulfonate anion
- Polyethylene dioxythiophene is used as the electrically conductive polymer.
- the polymer is applied to a carrier substrate in the form of its monomer with subsequent application of an initiator and / or catalyst or already in admixture with an initiator and / or catalyst.
- the application of the monomer (s) in admixture with the initiator and / or catalyst can be accomplished in any known conventional manner For example, by spin-coating, brushing, vapor deposition, by printing, (gravure, flexographic, screen, offset, digital and the like) by spraying, sputtering or roll coating techniques.
- Carrier substrates are, for example, carrier films, preferably flexible transparent plastic films, for example of PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC in question.
- carrier films preferably flexible transparent plastic films, for example of PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC in question.
- the carrier films preferably have a thickness of 5 to 700 ⁇ m, preferably 5 to 200 ⁇ m, particularly preferably 15 to 50 ⁇ m.
- metal foils for example Al, Cu, Sn, Ni, Fe or stainless steel foils having a thickness of 5-200 ⁇ m, preferably 10 to 80 ⁇ m, particularly preferably 20-50 ⁇ m, may also serve as the carrier substrate.
- the films can also be surface-treated, coated or laminated, for example, with plastics or painted.
- carrier substrates also paper or composites with paper, for example, composites with plastics with a basis weight of 20 - 500 g / m 2, preferably 40 - 2 are used 200 g / m.
- woven or nonwovens such as continuous fiber webs, staple fiber webs and the like, which may optionally be needled and / or calendered, can be used as the carrier substrates.
- fabrics or webs of plastics such as PP, PET, PA, PPS and the like, but it can also be woven or nonwovens made of natural, optionally treated fibers, such as viscose fibers are used.
- the nonwovens or fabrics used have a weight per unit area of about 20 g / m 2 to 500 g / m 2 . If necessary, the nonwovens or fabrics must be surface-treated.
- Fig.1 a special arrangement for applying the conductive polymers (as a mixture of monomer and initiator and / or catalyst) is shown.
- Fig.2 a further possibility of the application of the monomer and the initiator and / or catalyst is shown, in Figure 3 a possibility for applying two successive layers of the electrically conductive polymer, in Fig. 4 a scheme for the treatment of the washing liquid and in Fig. 5 and Fig. 5a an inventive embodiment of the application device with reservoir and separate provided as Zudosierüen storage containers.
- Fig. 1 to 3 2 means a storage vessel for the mixture of the monomer with the catalyst or for the monomer, 2a the catalyst application device (if only the monomer is provided in the storage vessel 2), 2b the storage vessel for the application of the second polymer layer, 3 6 a washing area with the following simultaneously or alternatively usable units 6a spray nozzles, 6b a brush or a felt and 6c an air knife and 7 an optional blow bar or a spray bar, 4 a squeegee, 5 a drying device (IR, UV or convection dryer) Dryer.
- Fig. 4 8 means water treatment (also adding ions in the form of salts), 9 a pressure control, 10 a pump, 11 the washing process, 12 a filter, 13 - 17 ion exchangers, 18 the sanitation.
- the storage vessel 2 or 2b consists of an outer tub 21 and an inner tub 22 with a return plate 22a.
- 23 means the feed of the monomer / initiator and / or catalyst and / or catalyst mixture from a supply (mixing) container 23a via a pump 23b and a filter 23c
- 24 means the outflow of the monomer / initiator and / or catalyst and / or catalyst mixture from the outer tub 22 in the reservoir.
- 3a means a dip cylinder and 3 the transfer cylinder.
- 25 denotes a distributor tunnel for the monomer / initiator and / or catalyst and / or catalyst mixture
- 26 the distributor plate of the distributor tunnel.
- Fig. 5a 27 means the reservoir for the monomer and 28 the reservoir for the initiator and / or catalyst and 29 the reservoir for the solvent.
- a reservoir 23a which is preferably double-walled and is temperature-controlled to set a corresponding temperature, via a pump 23b and a filter 23c in the temperature-controlled inner tub 22 of the reservoir 2 (off Fig. 1 ).
- the dispersion is evenly distributed via a distribution tunnel 25 and the distributor plate 26, which is provided with regularly arranged openings.
- the inner tub has on the inner surface of the shape of an approximately half-cylinder, wherein this surface is dimensioned so that the plunger cylinder 3 a can engage in a defined constant distance from the inner surface of the reservoir 2.
- the dip cylinder 3a engages with about 1/3 1/2 of its circumference into the dispersion conveyed into the inner tub.
- the temperature-controlled inner tub is dimensioned so that it on the side facing away from the drain 24 of the surrounding temperature-controlled outer tub side in about the dimension of a half-cylinder, but whose shape substantially continuing return plate up to a height of at least half of the diameter up to about 2 / 3 of the diameter of the submerged cylinder.
- the dip cylinder now takes the dispersion from the inner tub and transfers it to the transfer cylinder.
- the excess dispersion which is not absorbed by the transfer cylinder, now runs back into the outer trough 21 via the outside of the inner trough.
- that polymer dispersion fraction which passes over the doctor blade 4 (in FIG Figure 5 not shown) was not applied to the application tool, back into the outer tub.
- the temperature of the dispersion in the inner tub is kept correctly constant and air ingress is avoided. Furthermore, the temperature of the dispersion in the inner tub can be continuously monitored via a temperature sensor (in Figure 5 not shown).
- the drying of the applied dispersion is then carried out by the drying devices 5 or the washing process in the washing station 6 for the removal of solvent residues ( Fig.1 )
- the monomers or prepolymers are applied to form the electrically conductive polymers and polymerized in situ ( Fig. 2 . 3 . 5 and 5a ).
- Both monomer and initiator and / or catalyst are preferably provided in a solvent or dispersing agent, for example in an alcohol such as propanol or n-butanol.
- a catalyst for accelerating the reaction may be added, for example, a Ziegler-Natta catalyst, or a Pt catalyst, in which case optionally, the added amount of initiator and / or catalyst may be lower.
- the monomer provided in the storage vessel 2 and, if appropriate, analogous to in Fig. 5 illustrated embodiment of the application device are applied to the carrier substrate.
- the initiator and / or catalyst and / or catalyst or optionally the additional catalyst is provided in storage vessel 2a and applied to the monomer present on the carrier substrate, wherein an excess of initiator and / or catalyst is applied to complete polymerization of the polymer achieve, as described in detail in the following particularly preferred embodiment.
- the drying process, the washing process and optionally a further drying process (as described in more detail in the following particularly preferred embodiment of the process according to the invention) take place.
- the corresponding monomer is preferably mixed with the initiator and / or catalyst (and optionally with an additional catalyst) and applied to the carrier substrate (analogously Fig. 1 , wherein in the storage vessel 2, the monomer / initiator and / or catalyst mixture is provided).
- the preferred embodiment of the applicator has, as in Fig. 5a shown, in addition to the in Fig. 5 elements shown in each case a reservoir for the monomer and a separate reservoir for the initiator and / or catalyst or the initiator and / or catalyst or whl.
- Catalyst mixture and for the optionally additionally metered in solvent Preferably, the solvent is metered in via a viscosity regulator.
- the monomer / initiator and / or catalyst mixture is then in (strong) dilute solution in this case.
- the initiator / catalyst used is Fe (III) toluenesulfonate.
- Fe (III) toluenesulfonate is a free-radical initiator or catalyst which simultaneously initiates a redox reaction during the polymerization.
- the Fe (III) ion acts as an initiator and the toluenesulfonate forms the matrix in the conductive polymer.
- the polymer present on the carrier substrate after the polymerization is polyethylene dioxythiophene / toluenesulfonate (PEDT-TS, P-DOT).
- the Fa. Bayer in large excess compared to the monomer resp.
- Prepolymer used eg ethylenedioxythiophene, such as Baytron ® M or Baytron ® M-V2 from Bayer.
- the weight ratio of monomer or prepolymer to initiator and / or catalyst is thereby 1:20 - 1: 100, preferably 1:50 to 1:80.
- the excess initiator and / or catalyst ensures complete and safe reaction of the entire monomer even during shorter available reaction times, thus ensuring that no deleterious residues remain. Furthermore, optimum film formation is achieved by this excess of initiator and / or catalyst.
- the pure substances (monomer, initiator and / or catalyst) are used without the addition of further binders and / or additives.
- the polymerization takes place depending on the solvent used already at the time in which a temperature is reached, which causes evaporation of the solvent.
- the solvent for example, an alcohol such as propanol or n-butanol
- the undesired polymerization is controlled by metering in the monomer, which is highly diluted in the solvent
- an early polymerization can also be prevented by the exact control of the temperature in the storage containers and in the commissioned unit, wherein the immersion cylinder or transfer and application cylinder should possibly be cooled or heated.
- Fig. 5 and 5a designed applicator is therefore controlled by adjusting the ratios of the mixture components or the temperature of the reaction kinetics and at the same time achieves a uniform homogeneous application of the monomer solution or the monomer / initiator and / or catalyst mixture.
- the polymerization takes place at temperatures of 50-150 ° C., preferably at 80-120 ° C.
- Initiator and / or catalyst excess and optionally catalyst residues and other contaminating reaction products can also be removed in situ or optionally subsequently by treatment with a solvent, for example water, deionized water, deionized water, alcohols such as ethanol, propanols, butanols and the like or Water / solvent mixtures are removed from the layer.
- a solvent for example water, deionized water, deionized water, alcohols such as ethanol, propanols, butanols and the like or Water / solvent mixtures are removed from the layer.
- the initiator and / or catalyst excess is removed by water, which is treated, for example, by reverse osmosis, ion exchangers, distillation or physical water treatment plants.
- the reaction can be influenced during the washing process by a defined adjustment of the ion content of the water, in particular the content of alkali and / or alkaline earth metal ions. Attachment of the ions present in the water to the O atoms of the ethylenedioxythiophene units forms complexes, which changes the configuration of the macromolecules and thus shifts the band gap in the absorption spectrum and thus the absorption maximum.
- the conductivity is variable by this complex formation and can therefore be defined by the content of ions in the water defined.
- the water prepared as described above is therefore optionally adjusted to a defined ion content by addition of alkali and / or alkaline earth metal ions in the form of salts, for example sodium salts, for example NaCl or alkaline earth salts such as Mg salts, for example MgCl 2 .
- alkali and / or alkaline earth metal ions in the form of salts, for example sodium salts, for example NaCl or alkaline earth salts such as Mg salts, for example MgCl 2 .
- the washing process is preferably carried out by applying the selected washing liquid by means of one or more nozzle bars, wherein preferably pressure and angle of the washing liquid impinging on the coating are adjustable.
- the excess water on the polymer coating is removed by squeezing, wiping, drying, by suitable means such as squeezing devices, drying devices, air knife, or suction units and fed to a recycling cycle.
- the effluent from the process water is preferably circulated, where appropriate, if necessary, fresh water can be added.
- Wastewater saturated with initiator or initiator and catalyst is treated via a filter system and then via ion exchangers and / or by distillation.
- ion exchangers In order to ensure continuous operation, it is further preferred to use a group of several, preferably 1-5, ion exchangers, for example at least one ion exchanger being in operation, another in stand-by mode and another in regeneration mode.
- highly volatile constituents can also be removed by drying with an IR dryer, a convection dryer and the like.
- the electrically conductive polymer layers may each have a thickness of 0.1-50 ⁇ m, preferably 0.5-10 ⁇ m.
- thinner layers of 0.001 to 50 microns, preferably 0.05 to 10 microns are readily produced.
- the layers according to the invention are excellently conductive.
- the extensibility of the layer can be variably controlled depending on the polymerization process.
- the electrically conductive polymer layers are generally temperature-resistant, it may possibly temperature resistances of> 100 ° C can be achieved.
- a transparency of> 80% can be achieved with the electrically conductive polymer layers according to the invention.
- the electrically conductive polymers can also be pigmented, all known pigments being suitable. If the transparency is not to be significantly influenced, however, highly opaque or coloring pigments such as carbon black or graphite are not suitable.
- the proportion of pigments in the solid state can be up to 40%.
- the carrier material may be previously treated with a coupling agent to improve the adhesion of the conductive polymer used.
- a coupling agent to improve the adhesion of the conductive polymer used.
- the electrically conductive polymers can be present both on the entire surface as well as partially on the carrier material.
- the application of the electrically conductive polymers can be carried out according to one of the described embodiments of the method in the form of characters and patterns, flat or linear, wavy or zigzag and similar or analogous structures, such as guilloches, longitudinally and / or transversely to the machine direction of the substrate.
- Line-shaped or analogous structures have a conductivity directed in a preferred direction according to the orientation of the structures.
- these structures provide additional security against destruction by transverse cracks in this and possibly above and / or underlying layers, since these are prevented from tearing at the interstices. If such an electrically conductive layer is protected by an additional layer, for example a lacquer layer or by lamination, the gaps or recesses ensure improved sealing of the conductive polymer layer.
- these structures also represent a 2-dimensional coding.
- the electrically conductive polymeric layers are very stable mechanically and thermally, but may be sensitive to moisture, these layers are preferably not directly on the surface of the substrate.
- line-wave-shaped or zigzag-shaped structures or guilloches may be connected to increase the line cross-section via cross-connections which may have different widths or shapes and may also be arranged at different angles to the basic structure.
- the widths of the lines, waves or zigzag structures or guilloches can be, for example, 0.05-10 mm, preferably 0.1-0.3 mm, those of the cross-connections 0.5-100 mm, preferably 1-10 mm.
- the electroconductive monomers can be applied in any known conventional manner, for example by spin-coating, brushing, vapor deposition, by printing (gravure, flexo, screen, offset, digital, and the like) by spray, sputter, or roller application techniques.
- a solvent-soluble paint or a soluble paint can be applied to the carrier substrate or any layers already thereon. Subsequently, the conductive polymer is applied to this layer, whereupon the soluble color in the uncoated areas is removed by means of the appropriate solvent, optionally with mechanical assistance.
- the partial application can also after the in the DE 100 25 522 A1 described method.
- the electrically conductive polymer layer can also be adjusted to be adhesive or releasable.
- the time being to apply a layer of the electrically conductive polymer and then to apply a further layer of the electrically conductive polymer by in situ polymerization.
- the electrically conductive polymer layers according to the invention can also be used preferably in conjunction with an inorganic one metallic or pigmented conductive layer can be applied particularly advantageous. Not only is there an improvement in the electrical conductivity of the coated substrate but also an additional assurance of proper function and identifiability.
- a multilayer construction of a full-area or partial layer of a conductive polymer having linear, wavy, and the like structures of the same polymer printed thereover results in different conductivities in the different directions, for example parallel or cross-machine direction, but also at any angle to the machine direction.
- the full-surface polymeric conductive base layer is made, for example, by a corresponding depth-variable gravure cylinder, in different thickness, thereby angle-dependent conductivities are achieved.
- the polymeric conductive primer layer and the second polymeric conductive layer deposited thereover may also be separated by an insulator layer.
- the electrically conductive layer (s) of polymer (s) are not in direct contact with metallic layers and are separated therefrom by an insulator layer.
- the electrically conductive polymer layers as well as, if appropriate, the additional inorganic metallic and / or pigmented electrically conductive layers, can be coded as patches and thus also be applied in a machine-readable and / or structured manner. Furthermore, the electrically conductive polymer layers can subsequently be embossed inline or offline.
- the carrier substrate may already have functional or decorative layers, or further layers may be applied after the conductive layer has been applied.
- the carrier substrates may additionally have a lacquer layer, which may be unstructured or structured, for example embossed.
- the lacquer layer can be, for example, a release-capable transfer lacquer layer, it can be crosslinked or crosslinkable by radiation, for example UV radiation, and can be scratch-proof and / or antistatic.
- Both aqueous and solid coating systems in particular lacquer systems based on polyester acrylate or epoxy acrylate, are rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems which are conventionally and / or reactively curing and / or can be radiation-curing.
- compositions in each case a wide variety of compositions can be used.
- the composition of the individual layers may in particular vary according to their purpose, that is to say whether the individual layers serve exclusively for decorative purposes or should be a functional layer or whether the layer should be both a decoration layer and a functional layer.
- These layers may be pigmented or unpigmented.
- pigments all known pigments such as titanium dioxide, zinc sulfide, kaolin, ITO, ATO, FTO, aluminum, chromium and silicon oxides and colored Pigments are used. In this case, solvent-based coating systems and systems without solvents can be used.
- Suitable binders are various natural or synthetic binders.
- the functional layers may have certain magnetic, chemical, physical and also optical properties.
- paramagnetic, diamagnetic and also ferromagnetic substances such as iron, nickel and cobalt or their compounds or salts (for example oxides or sulfides) can be used.
- Particularly suitable for use in conjunction with the electrically conductive polymer layers according to the invention are magnetic pigment paints with pigments based on Fe oxides, iron, nickel cobalt and their alloys, barium or cobalt ferrite, hard and soft magnetic iron and steel grades in aqueous or solvent-containing dispersions.
- suitable solvents are i-propanol, ethyl acetate, methyl ethyl ketone, methoxypropanol and mixtures thereof.
- the pigments are preferably incorporated in acrylate polymer dispersions having a molecular weight of from 150,000 to 300,000, in nitrocellulose, acrylate-urethane dispersions, acrylate-styrene or PVC-containing dispersions or in solvent-containing dispersions of this type.
- the optical properties of the layer can be visualized by visible dyes or pigments, luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region, effect pigments, such as liquid crystals, pearlescent, bronzes and / or multilayers Color change pigments and heat-sensitive colors or pigments influence. These can be used in all possible combinations.
- phosphorescent pigments can also be used alone or in combination with other dyes and / or pigments.
- a brown magnetic paint can be metallic, e.g., by adding metals in its hue, e.g. be set silvery.
- the ink or lacquer used can be soluble in a solvent, preferably in water, but it can also be a dye soluble in any solvent, for example in alcohol, esters and the like become.
- the color or the colored lacquer can be customary compositions based on natural or artificial macromolecules.
- the color may be pigmented or unpigmented.
- pigments all known pigments can be used. Particularly suitable are TiO 2 , ZnS, kaolin and the like.
- a soluble color layer may optionally be removed after application of another layer in the process according to the invention by a suitable solvent adapted to the composition of the color layer in order to be able to produce codings in the form of characters and / or patterns of any possible type.
- the color layer is removed by a suitable solvent, which is adapted to the composition of the color layer.
- a suitable solvent which is adapted to the composition of the color layer.
- the paint is water-soluble.
- the separation can be supported by mechanical action.
- insulator layers can be applied.
- insulators for example, organic substances and their derivatives and compounds, for example, paint and varnish systems, e.g. Epoxy, polyester, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems which may be radiation-curable, for example by heat or UV radiation.
- paint and varnish systems e.g. Epoxy, polyester, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems which may be radiation-curable, for example by heat or UV radiation.
- Such layers can be used in particular in the production of multilayer structures, for example for printed circuit boards, between two or more electrically conductive polymer layers and / or electrically conductive metallic and / or pigmented layers which have to be separated from one another.
- These layers may be applied by known methods such as sputtering, sputtering, printing (e.g., gravure, flexo, screen, offset, digital printing, and the like), spraying, electroplating, and the like.
- the thickness of the functional layers is generally about 0.001 to 50 microns, preferably 0.1 to 20 microns.
- partial or full-surface metallic layers may be present on the carrier substrate or subsequently applied.
- This layer consists of a metal, a metal compound or an alloy, wherein these metallic layers can also represent inorganic electrically conductive layers.
- the metal layer layers of Al, Cu, Fe, Ag, Au, Cr, Ni, Zn and the like are suitable.
- metal compounds For example, oxides or sulfides of metals, in particular TiO 2 , Cr oxides, ZnS, ITO, ATO, FTO, ZnO, Al 2 O 3 or silicon oxides are suitable.
- Suitable alloys are, for example, Cu-Al alloys, Cu-Zn alloys and the like.
- All of these layers can be applied over the entire area as well as partially, with registration and register accuracy, if appropriate also at least partially overlapping with the already existing layers.
- a blow bar can be located, with a plurality of nozzles arranged over the entire width. Through these nozzles filtered air with defined humidity, optionally heated or cooled, directed at the same speed on the printing cylinder, whereby the thin layers dry on the cylinder and can not be applied to the carrier substrate.
- an IR drying device situated over the entire width can also be used.
- created Tonungsreste can also be removed for example by using a plasma (low pressure or adjaplasma-), Corona or flame process.
- a plasma low pressure or adjaplasma-
- Corona flame process
- energetic plasma For example, Ar or Ar / O 2 plasma, the surface of Tonungsresten of the printing inks is cleaned.
- the surface is activated.
- terminal polar groups are generated on the surface. This improves the adhesion of metals and the like to the surface.
- a thin metal or metal oxide layer can be applied as adhesion promoter, for example by sputtering or vapor deposition.
- adhesion promoter particularly suitable are Cr, Al, Ag, Ti, Cu, TiO 2 , Si oxides or chromium oxides.
- This adhesion promoter layer generally has a thickness of 0.1 nm to 5 nm, preferably 0.2 nm to 2 nm, particularly preferably 0.2 to 1 nm.
- the product is therefore optionally suitable for packaging as a security element in data carriers, in particular value documents such as identification cards, banknotes or labels, seals and the like, but also as packaging material, for example in the pharmaceutical and food industry, for example in the form of blister foils, cartons, covers, Foil packaging and the like suitable.
- Such products are also particularly suitable for applications in the electronics industry, for example as printed circuit boards, RF antennas for transponders and the like, displays, flexible circuits, medical devices, electrode assemblies, as heatable films, for example for windshields, as a transparent reflection layer under holograms and / or structured layers and the like. Further, because of their excellent optical properties, they can be used as a "high refractive index" layer, as decorative or optical elements, for example in architecture and the like.
- the substrates or film materials are preferably cut into strips and threads, wherein the width of the strips or threads may preferably be 0.05-10 mm.
- Example 1 (not according to the invention):
- a carrier film of PET with a thickness of 50 microns which is already partially coated with an optically active layer, and on a commercial adhesion promoter (A 1120, Fa. OSI)) is applied, from a storage vessel via a transfer roller, a dispersion of 2% Polyethylendioxythiophen (particle size 100 nm in the dispersion) with 2% polystyrene sulfonate in water / i-propanol as a dispersant over the entire surface in a layer thickness of 3 microns applied. Subsequently, the applied polymer layer is dried at 110 ° C.
- the film thus produced has a conductivity of 800 ⁇ / square, the conductive layer has a transparency of 87%
- a mixture of ethylenedioxythiophene and Fe (III) toluenesulfonate as initiator in a weight ratio of 1:60 is then applied by gravure printing at 110 ° C. and polymerized. This mixture is polymerized in situ and is subsequently used to remove catalyst residues treated with water. Subsequently, the layer is dried and applied a conventional protective lacquer layer.
- the conductive film thus produced has a conductivity of 220 ⁇ / square and the two conductive layers together have a transparency of 82%.
- a subsequently applied to the film in a known manner fluorescent coating layer has no effect on the conductivity or transparency of the remaining free areas of the conductive layers.
- Example 2 Analogously to Example 1, a partial layer made from Baytron ® M and Baytron ® CB-40 in a weight ratio of 1: 60 was dissolved in n-butanol according to the in Fig. 1 and 5a described method applied to a 6 micron polyester film.
- the partial layer has a line-shaped structure of 0.1 mm width at a distance of 0.1 mm.
- the substrate is cut into threads of a width of 1 mm, whereby an average of 5 line structures are present on a thread.
- the directional conductivity is 215 ⁇ / square.
- the film produced according to Example 3 is coated with a 10 ⁇ m PET film having a 0.5 ⁇ m partial layer consisting of a magnetic printing ink based on Fe 3 O 4 in an acrylate polymer dispersion and a 0.2 ⁇ m layer of a fluorescent printing ink laminated by means of a commercially available laminating adhesive.
- the conductivity was 215 ⁇ / square, the magnetic properties were determined to be 330 nW / m with a coercivity of 250 Oerstedt.
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- Business, Economics & Management (AREA)
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- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Rolls And Other Rotary Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Insulated Conductors (AREA)
- Silicon Polymers (AREA)
Claims (8)
- Procédé de fabrication d'éléments de sécurité qui présentent un substrat support sur lequel sont déposées des couches électriquement conductrices, caractérisé en ce que le monomère éthylènedioxythiophène (EDT) est déposé sur le substrat support et polymérisé in situ en utilisant l'amorceur toluènesulfonate de Fe(III), le monomère et l'amorceur étant déposés selon un ratio en poids allant de 1:20 à 1:100 et le monomère étant déposé d'abord, suivi du dépôt de l'amorceur et/ou du catalyseur, ou bien déjà présent sous forme de mélange avec l'amorceur et/ou le catalyseur, afin de former ainsi une couche électriquement conductrice en polyéthylènedioxythiophène (PEDT) qui est stabilisée par l'anion de toluènesulfonate non associé à la liaison polymère.
- Procédé selon la revendication 1, caractérisé en ce qu'il utilise en plus un catalyseur.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'amorceur et/ou les restes de catalyseur et/ou d'autres produits réactionnels indésirables sont éliminés par lavage avec de l'eau traitée par osmose inverse, par passage sur une résine échangeuse d'ions, par distillation et/ou dans des installations de traitement physique et ayant une teneur définie en ions de métaux alcalins ou alcalino-terreux.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'eau utilisée pour le lavage circule en circuit fermé et est retraitée par filtration, passage sur une résine échangeuse d'ions et/ou distillation.
- Procédé selon l'une des revendications 3 à 4, caractérisé en ce que de l'eau fraîche traitée par osmose inverse, par passage sur une résine échangeuse d'ions, par distillation et/ou dans des installations de traitement physique est alimentée si nécessaire dans le circuit d'eau de lavage.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'une étape de lavage finale est effectuée avec de l'eau fraîche traitée par osmose inverse, par passage sur une résine échangeuse d'ions, par distillation et/ou dans des installations de traitement physique.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'opération de lavage se fait en ligne ou hors ligne.
- Procédé selon l'une des revendications 1 à 7, caractérisé en ce que des couches fonctionnelles et/ou décoratives sont déjà présentes sur le substrat support et/ou y sont déposées par la suite.
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AT6142002 | 2002-04-22 | ||
AT6142002 | 2002-04-22 | ||
CH2702003 | 2003-02-20 | ||
CH2702003 | 2003-02-20 | ||
AT3082003A AT504538B1 (de) | 2003-03-03 | 2003-03-03 | Substrate mit elektrisch leitfähigen schichten |
AT3082003 | 2003-03-03 |
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EP1357226A2 EP1357226A2 (fr) | 2003-10-29 |
EP1357226A3 EP1357226A3 (fr) | 2004-01-07 |
EP1357226B1 true EP1357226B1 (fr) | 2010-08-11 |
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EP03008537A Expired - Lifetime EP1357226B1 (fr) | 2002-04-22 | 2003-04-12 | Substrats avec couches électriquement conductrices |
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EP (1) | EP1357226B1 (fr) |
AT (1) | ATE477371T1 (fr) |
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US8048605B2 (en) | 2001-03-16 | 2011-11-01 | Datalase Ltd | Laser-markable compositions |
ES2278008T5 (es) | 2001-03-16 | 2011-11-18 | Datalase Ltd | Composiciones que pueden marcarse por láser y procedimiento de formación de imágenes por láser. |
AT500871B1 (de) * | 2003-06-17 | 2007-03-15 | Hueck Folien Gmbh | Sicherheitselemente mit visuell erkennbaren und maschinenlesbaren merkmalen |
JP2007500090A (ja) | 2003-07-30 | 2007-01-11 | データレイズ・リミテッド | レーザマーキング可能な組成物 |
AT500289A1 (de) * | 2003-12-29 | 2005-11-15 | Hueck Folien Gmbh | Substrate mit elektrisch leitfähigen schichten für technische anwendungen |
WO2006042568A1 (fr) * | 2004-10-20 | 2006-04-27 | Hueck Folien Ges.M.B.H | Substrats comportant des couches electroconductrices |
EP1841004A1 (fr) | 2006-03-29 | 2007-10-03 | Hueck Folien Ges.m.b.H | Antenne pour transpondeur sur un substrat à revêtement antistatique |
KR102003530B1 (ko) | 2011-07-08 | 2019-10-17 | 헤레우스 프레셔스 메탈스 게엠베하 운트 코. 카게 | 적층체의 제조 공정 및 이로부터 얻어지는 적층체 |
KR20160005848A (ko) * | 2014-07-07 | 2016-01-18 | 한국전자통신연구원 | 무칩 알에프 태그 기반의 보안용 인쇄용지 및 그 제조방법 |
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WO2002005360A1 (fr) * | 2000-07-07 | 2002-01-17 | Siemens Aktiengesellschaft | Procede pour produire et structurer des transistors organiques a effet de champ (ofet) |
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---|---|---|---|---|
DE3915638B4 (de) * | 1989-05-12 | 2006-06-08 | Giesecke & Devrient Gmbh | Sicherheitsdokument mit darin eingebettetem Sicherheitselement mit visuell und maschinell prüfbaren Kennzeichen und Sicherheitselement für ein Sicherheitsdokument |
EP0615257B1 (fr) * | 1993-03-09 | 1999-06-02 | Koninklijke Philips Electronics N.V. | Méthode de fabrication d'une structure laminée ayant une couche métallique sur une couche de polymère conducteur |
US6197418B1 (en) * | 1998-12-21 | 2001-03-06 | Agfa-Gevaert, N.V. | Electroconductive glass laminate |
DE19937262A1 (de) * | 1999-08-06 | 2001-03-01 | Siemens Ag | Anordnung mit Transistor-Funktion |
EP1079397A1 (fr) * | 1999-08-23 | 2001-02-28 | Agfa-Gevaert N.V. | Méthode de formation d'un motif conducteur sur un substrat |
DE60033012T2 (de) * | 1999-09-10 | 2007-09-13 | Koninklijke Philips Electronics N.V. | Leitende struktur basierend auf poly-3,4-alkendioxythiophen (pedot) und polystyrolsulfonsäure (pss) |
DE10025522B4 (de) * | 2000-05-18 | 2004-05-13 | Technische Universität Dresden | Verfahren zur strukturierten Abscheidung leitfähiger Polymerer |
-
2003
- 2003-04-12 AT AT03008537T patent/ATE477371T1/de active
- 2003-04-12 DE DE50312962T patent/DE50312962D1/de not_active Expired - Lifetime
- 2003-04-12 EP EP03008537A patent/EP1357226B1/fr not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002005360A1 (fr) * | 2000-07-07 | 2002-01-17 | Siemens Aktiengesellschaft | Procede pour produire et structurer des transistors organiques a effet de champ (ofet) |
Non-Patent Citations (2)
Title |
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BECKER E. ET AL: "A new structuring Technique for Polymer Integrated Circuits", PROCEEDINGS OF: FIRST INTERNATIONAL IEEE CONFERENCE ON POLYMERS AND ADHESIVES IN MICROELECTRONICS AND PHOTONICS, 21 October 2001 (2001-10-21), pages 95 - 97 * |
PEI Q. ET AL: "Electrochromic and highly stable poly(3,4-ethylenedioxythiophene) switches between opaque blue-black and transparent sky blue", POLYMER, vol. 35, no. 7, 1994, pages 1347 - 1351 * |
Also Published As
Publication number | Publication date |
---|---|
DE50312962D1 (de) | 2010-09-23 |
ATE477371T1 (de) | 2010-08-15 |
EP1357226A3 (fr) | 2004-01-07 |
EP1357226A2 (fr) | 2003-10-29 |
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