WO2009098456A1 - Printing ink for value or security documents - Google Patents
Printing ink for value or security documents Download PDFInfo
- Publication number
- WO2009098456A1 WO2009098456A1 PCT/GB2009/000315 GB2009000315W WO2009098456A1 WO 2009098456 A1 WO2009098456 A1 WO 2009098456A1 GB 2009000315 W GB2009000315 W GB 2009000315W WO 2009098456 A1 WO2009098456 A1 WO 2009098456A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- printing
- ink
- particle size
- polycarbonate polyurethane
- dispersion
- Prior art date
Links
- 238000007639 printing Methods 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 26
- 239000004417 polycarbonate Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000002966 varnish Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 13
- 239000013530 defoamer Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 41
- 239000000976 ink Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 21
- 239000002562 thickening agent Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 13
- 229920003009 polyurethane dispersion Polymers 0.000 description 13
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- -1 alkylene diol Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 239000003906 humectant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001010 compromised effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000010022 rotary screen printing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 240000000254 Agrostemma githago Species 0.000 description 1
- 235000009899 Agrostemma githago Nutrition 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000272194 Ciconiiformes Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 231100000230 acceptable toxicity Toxicity 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to a printing ink or varnish, especially a screen printing ink or varnish, suitable for use on value or security documents, such as bank notes, securities and the like.
- the documents, and thus the inks on them should be resistant to fading or colour change, so that, at worst, any such fading or colour change is imperceptible to the average eye. It is, moreover, a prime requirement that the coating composition should be harmless to humans and domestic animals. Hence, any ink or varnish used on them should, when cured, be robust, water-resistant and flexible. Moreover, certain States are moving away from the use of paper as the substrate for bank notes, and so ideally any ink or varnish for such use should be useable on plastics as well as paper.
- the coating composition should have a viscosity appropriate to the intended printing method, it should have acceptable toxicity, should ideally minimise the use of unsafe materials in the course of manufacture, even if they are not present in the finished product, and it should allow the use of a wide variety of pigments or dyes in order to maximise the possible colours for printing.
- the coating composition should be made available to the end user in as simple a form as possible, which, in practice, means in a single pack, with a storage stability measured in months, ideally at least 6 months, still better at least 12 months.
- N-methylpyrrolidone which is a very common solvent often used in the preparation of polyurethane dispersions, has had for some years a question mark over its safety, and it would be highly desirable to avoid its use, whilst still maintaining the useful properties that it imparts to the finished product.
- Solvent free emulsion polymerised polymers contain free surface active agent, which then aggravates the requirement for water-resistance, since a composition applied in solution or dispersion in water may, unless it undergoes a fundamental change, also be easily removable in water or water-based fluids.
- Polyurethane dispersions are, in general, produced by the aqueous dispersion of pre- formed polymers, which are subsequently dispersed in water.
- the isocyanate terminated prepolymer In order to facilitate the aqueous dispersion step the isocyanate terminated prepolymer must have a workable viscosity/molecular weight. This viscosity regulation is achieved by a solvent diluent, commonly N-methylpyrrolidone, which remains in the final dispersion.
- the pre-polymer is then neutralised and transferred to water where spontaneous particle formation occurs. Chain extension is carried out at this stage, producing a high molecular weight polyurethane dispersion. No free surface active agent is usually required, which reduces re-dispersability on hot washing.
- WO 03/020835 describes a water-based screen printing ink composition having (a) an acrylic or urethane-acrylic copolymer emulsion; (b) a cross- linker; (c) optionally a catalyst; (d) optionally pigments; and (e) optionally additives, characterized in that said cross-linker comprises at least two different chemical functionalities within the same molecule, wherein a first of said functionalities is chosen such as to form a covalent link with said polymer prior to printing and a second of said functionalities is selected to effect cross-linking of said polymer to cure the printed ink and that the acrylic or urethane-acrylic copolymer emulsion is selected from the group having self-cross-linking properties.
- the unmodified acrylic or urethane-acrylic copolymer emulsions used in WO 03/020835 produce inadequate chemical and hot wash resistance. Reacting via a two step process with bi-functional silanes increases chemical and hot- wash resistance. However, these compositions hydrolyse with time in aqueous systems, reacting with acid groups in the polymer, after an induction period of up to two days. This reaction leads to an upward drift of pH, which may increase viscosity and reduce dispersion stability. The drift may be reduced, but not eliminated, by adjustment to near neutrality by the controlled addition of volatile organic amines. Organosilanes may also self condense with time making them unavailable for further reaction.
- the silanes also can react with pigments in competition with reaction with the polymer: this necessitates pigment pre- treatment, for example with a fiuorochemical surfactant.
- the increase in acid value also reduces base resistance.
- the polyurethane dispersions used in the present invention exhibit very unique film properties, especially in terms of mechanical properties ideally suited for this high performance surface coating application.
- the film particles In order to develop a film with the requisite mechanical and resistance properties the film particles must coalesce.
- the high molecular weigh polymer chains are contained within particles. Particles need to deform and coalesce to attain efficient interpenetration of the chains to result in a coherent film.
- porous substrates may be physically interpenetrated by these very small broadly distributed dispersions, producing enhanced adhesion, hi the case of non-coated polymer films, solvation of the polymer by the cosolvent is required to produce interpenetration and adhesion.
- Such polyurethanes are known. See, for example, US2007/0167565, US 5,349,041, US 5,334,690, EP 0837083, and EP 0969029. They have been used for a variety of purposes, including as automotive and other coatings. However, although US 5,334,690 suggests their use as printing inks, they have not been used for security printing, and we have discovered that, in order to be used successfully for such printing, they must have a particle size within a specific range and a certain minimum acid value. They should also be free from free isocyanate groups.
- the present invention consists in a method of printing a value document, in which a printing ink or varnish comprising a dispersion of a resin is applied to the document, characterised in that the dispersion is an aqueous dispersion of a polycarbonate polyurethane and/or a polyether or polyester polycarbonate polyurethane copolymer having a particle size range from 10 to 400 nm and an acid value no greater than l0 mg KOH/g.
- the value documents to which the present invention may be applied include bank notes, passports, gift tokens/vouchers, product authentication certificates, securities certificates etc., as well as any other form of document, whether printed on paper or an a plastics substrate, having similar security requirements to those of bank notes. However, it is thought that the invention will be of greatest value in relation to banknotes.
- the polyurethanes of the present invention may be prepared by the reaction of a polyisocyanate with a diol or polyol.
- the preferred polyols are polycarbonate polyols, although other polyols such as polyether or polyester polyols may be included.
- the polycarbonate polyols may be produced via an ester interchange reaction or alcoholysis of diethyl carbonate or diphenyl carbonate with a polyol, preferably an alkylene diol. Examples of these diols are 1,4-butanidiol, 1,6-hexanidiol, or an alkylene ether diol e.g. triethylene glycol, glycerol or tripropylene glycol.
- Polyols with three or more hydroxyl groups such as trimethylolpropane, glycerol and pentaerythritol can be incorporated for preparing polycarbonate polyols.
- Mixtures of polycarbonate polyols may be utilised and the polycarbonate backbone may be aromatic or aliphatic, but is preferably aliphatic in nature. It may also be linear or branched.
- diisocyanate compounds include, but are not limited to, hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 4,4- dicyclohexylmethane diisocyanate (H12MDI), 2,24-trimethyl hexamethylene diisocyanate,2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), trimethylhexamethylene diisocyanate (TMDI), diphenylmethane diisocyanate (MDI), tetramethylene diisocyanate (TMXDI), and xylene diisocyanate (XDI).
- HMDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- H12MDI 4,4- dicyclohexylmethane diisocyanate
- TDI 2,24-trimethyl hexamethylene diisocyanate
- the neutralising agent for the aqueous dispersion stage should preferably be a low volatility organic amine, e.g. diethanolamine, diethylamine, triethylamine, morpholine or triethylamine.
- Triethylamine is an example of a preferred amine for this application.
- Covalently cross-linkable functionalities may be built in within the polymer chains to further enhance mechanical and chemical resistance properties.
- Suitable polycarbonate backboned polyurethane dispersions are available as Incorez W835/360, W835/364, W835/256 and W835/140 ex (Industrial Copolymers), U9160vp, U9152VP and U6150VP ex (Albedingk Boley).
- the high molecular weight anionic polyurethane dispersion has polymer chains arranged with softer and harder segments. Softer segments arise from high molecular weight polyol components, while the harder segments arise from diisocyanates, low molecular weight diols and urethane urea bond sequences. The mixing of these segments yields specific film properties, which may be uniquely tailored to this coating application.
- the polyurethanes of the present invention are preferably polydisperse, having an average particle size of from 40 to 100 nm, more preferably from 60 to 90nm and most preferably about 80 nm.
- the overall range of particle sizes is from 10 to 400 nm, more preferably from 20 to 200 nm.
- the acid value of the polyurethane is no greater than 10 mg KOH/g, preferably no greater than 9 and more preferably from 3 to 8.
- polyurethane dispersion should form a polymer film highly resistant to plasticisation and hydrolysis - if these happen, the wet tensile strength will be reduced and the film will be susceptible to chemical and physical attack.
- Polycarbonate polyurethanes are both tough and very hydrolytically stable, and so meet these requirements. As is well known in the art, by the incorporation of specialist functional groups, flexibility and elongation can be maintained. Other polyols, such as polyether polyols, may be incorporated to increase hydrolytic stability still further.
- Such a film preferably has a Persoz hardness of 150 to 300 seconds, more preferably from 180 to 260 seconds.
- Such a film preferably has an ultimate tensile strength of from 10 to 50 MPa, more preferably from 13 to 30 MPa.
- the amount of polyurethane may vary over a wide range as is well known in the art. However, in general, we prefer that it should comprise from 60 to 88%, more preferably from 60 to 75%, of the ink or varnish composition.
- the polyurethane will normally be supplied as a dispersion, in which case a solvent may already be present. If there is no solvent or insufficient solvent, then a solvent should be added.
- suitable solvents include 2-(2-butoxyethoxy)- ethanol, tripropylene glycol monomethyl ether, N-ethylpyrrolidone and dipropylene glycol monomethyl ether.
- the amount of solvent is preferably sufficient to reduce the minimum film- forming temperature of the ink or varnish to a value in the range from 0 to 40 0 C.
- the total solvent preferably comprises from 3 to 10, more preferably from 5 to 9%, of the ink or varnish composition.
- some of the added cosolvent may be replaced by a humectant at a level from 1 to 5%, to reduce drying on the screen.
- humectants may be based on glycols, polyglycol, polyethers, acid amides, urea and polysaccharides (such as sorbitol), which may be used on their own or in combination. Examples of preferred humectants are Miraplast SCR- 47 from Bohner Chemie and diethylene glycol. Glycols like diethylene glycol are capable of lowering the minimum film forming temperature. Humectants, particularly the glycols, may also be added to improve low temperature and freeze/thaw stability.
- the overall water content of the printing ink or varnish composition (including not only any added water, but also any water present in the other components of the composition) is preferably from 35 to 45% by weight, in order to achieve optimal printing without excessive substrate cockle.
- a defoamer may be incorporated.
- Preferred defoamers include polysiloxanes, polyether modified polydimethyl siloxane, polyether mixed with polyether siloxane and hydrophobic solids, such as Tego Foamex 805, 810, 812N, 822, 825 and 840 or Byk 011, 019, 024.
- the amount of defoamer is preferably from 0.5 to 2.0% of the composition.
- Ancillary de-foaming and flow modifying agents may be included, for example:- polyoxyethylenated polyoxypropylene glycol, tertiary acetylenated glycols (e.g.
- the amount is preferably in the range from 0.1 to 2%, more preferably from 0.1 to 0.5% by weight of the composition.
- thickener it may also be necessary to include a thickener, depending on the intended printing technique.
- thickeners and the amounts thereof are well known to those skilled in the art.
- suitable thickeners include Bentone DE, Reolate 125 ex Elementis, Acrysol RM-8W, Byk 420E, and Byk 425 ex Bky Chemie. It was found that the blend that was most preferred should include modified urea and or polyurethane urea at 0.1 to 0.6 %. These are available as Byk 420E and Byk 425.
- the composition should include a pigment, which may be chosen from any of those known for use in printing inks.
- the amount of pigment is preferably from 15 to 19% of the composition for screen printing applications, hi general, we prefer that the weight ratio of pigment to binder (including the polyurethane and any other binder present) should be from 1 : 1.1 to 1 : 1.5, in order to optimise abrasion resistance and control finish.
- a pigment dispersant is important to minimise settlement and improve re-dispersion.
- the selected dispersant is preferably an amine neutralised polyacrylate, which is particularly suited because, on drying, amine is lost and film water resistance is not compromised.
- Other dispersants based on chemistries such as styrene maleic anhydride (e.g. Disperse Ayd W22) may be used.
- polycarbodiimide in the composition.
- examples of polycarbodiimides are given, for example, in US 5,258,481 and 5,047,588, the disclosure of which is incorporated herein by reference.
- the emulsion grades of polycarbodiimides are to be preferred for maximum shelf life.
- the preferred polycarbodiimide is Carbodelite (ex Nisshinbo Industries). Where a polycarbodiimide is used, the amount is preferably from 1.0 to 2.5% of the composition.
- compositions of the present invention may be used in any printing technique for printing on a substrate, but are especially suitable for rotary screen printing.
- compositions of the present invention are only able to penetrate the surface of the substrate, and thus adhere to it, if they are of appropriate coating viscosity and if their surface energy is low enough to achieve adequate wetting. This is a precondition for the very fine polyurethane particles penetrating the substrate surface layer. The extent of the penetration is dependent on the surface treatment and the internal substrate structure.. Surface coatings, paper compression and internal binders may reduce penetration, in which case adhesion may be compromised. Alteration of co-solvent, wetting and other dispersion additives may alleviate the problem, as is well known in the art. Polymer based banknote substrates are generally coated with print receptive matt layers, with unprinted areas remaining as clear windows. These coatings are commonly approximately 5-7 ⁇ m in thickness with a surface tension of 44mN/m. The compositions of the present invention are capable of wetting and penetrating the surface coated layer, producing good adhesion.
- the printing ink or varnish should be free from compounds which fluoresce under ultraviolet, should not yellow when heated to 150°C, should meet health and safety criteria (lack of irritancy, toxicity and sensitisation), and should have a flash point greater than 100 0 C.
- the invention also provides value documents, especially bank notes, printed by the method of the present invention.
- Incorez W835/360 an aliphatic polyester polycarbonate polyurethane
- 2-(2- butoxyethoxy)ethanol a cosolvent
- the mixture was immediately filtered twice, each time through a 100 micron filter, after which it was filled into containers, to give a rotary screen ink, acid value 8mg. KOH/g, pH 9, particle size 30-200 nm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, pH7-8, particle size 0.5-1.5 microns.
- Thickener blend 2 was prepared by mixing the following components using a similar procedure to that described in Example 1.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 20mg. KOH/g, pH 7-8, particle size 50-250 nm.
- Example 4 contains N-methylpyrrolidone in the polyurethane dispersion, and is also a potential sensitizer because of the presence of the bi-functional organosilane.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a flat-bed screen ink, acid value 8.0 mg KOH/g, pH 8.5-9.0, particle size 20-100nm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, pH 9, particle size 40- lOOnm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, , pH 9, particle size 40- lOOnm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, , pH 9, particle size 40- lOOnm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8-9 mg KOH/g, pH 8-9, particle size 40-100nm.
- Example 2 Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8-9 mg KOH/g, pH 8-9, particle size 40-lOOnm.
- Neocryl XKl 1 NeoResins Neocryl XKl 1 NeoResins.
- Neo Pac E- 125 NeoResins
- Rotary screen printed value documents (Banknotes ), were also subjected to the full E.C.B. battery of 16 Chemical tests. All the Examples quoted passed the tests at least to the minimum standard.
- ink systems were assessed via storage at room temperature and at 4O 0 C in tightly closed glass containers. Viscosity measurements were made to monitor thickening and changes in structure. The inks were printed and tested for hot washing machine resistance as a function of storage time. The hot washing machine test is very sensitive to changes due to aging of the ink system. Solvent resistance tests based on number of rubs have been used in the past to assess ageing of ink systems. These measurements were found not to correlate with hot washing tests.
- a score of 4 out of 4 on the test represents no removal of the printed security feature and 0 represents complete removal.
- the test is subject to some variation and is usually repeated on 5 samples and the results averaged out.
- the structural changes in the inks were assessed using a DIN 4 flow cup at 22 0 C and a Bohlin CS Rheometer using cup and bob geometry. Storage tests were suspended if the times on the flow cup had increased by more than 5 seconds. Only samples that passed this assessment were hot washing machine tested. It is to be noted that samples settle to varying degree and they must be remixed until homogeneous before viscosity measurement or printing. The results are shown in Table 2.
- Sample prints were prepared by Screen printing (77T mesh), onto a range of banknote type papers. Prints were also produced via coating with a no 3 bar. All the prints were thoroughly hot air dried. The prints were left for 8 hours and tested with solvents applied with cotton buds. The number of low pressure double rubs was recorded. The prints were also cross-hatch tape tested (Tessa tape). The results were recorded on a 0-4 scale, with 4 representing no removal.
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Abstract
A value document, such as a banknote, is printed using a printing ink or varnish comprising an aqueous dispersion of a preferably aliphatic polycarbonate polyurethane and/or a polyether or polyester polycarbonate polyurethane copolymer having a particle size range from 10 to 400 nm and an acid value no greater than 10 mg KOH/g.
Description
PRINTING INK FOR VALUE OR SECURITY DOCUMENTS
The present invention relates to a printing ink or varnish, especially a screen printing ink or varnish, suitable for use on value or security documents, such as bank notes, securities and the like.
All security documents are required to have good stability and durability. However, in the case of bank notes, these requirements are extreme, as bank notes are routinely and unthinkingly abused by the public - they are folded, crushed, crumpled, subjected to abrasion, exposed to weather, exposed to bodily fluids such as perspiration and others even less acceptable, laundered, dry-cleaned, ironed or torn - and, after having been subjected to this, they are expected to be as legible as when they started. Furthermore, it is essential that the documents should have a reasonable life, measured at least in months and ideally years, despite being passed from hand to hand and possibly suffering the above-mentioned abuse. During this time, the documents, and thus the inks on them, should be resistant to fading or colour change, so that, at worst, any such fading or colour change is imperceptible to the average eye. It is, moreover, a prime requirement that the coating composition should be harmless to humans and domestic animals. Hence, any ink or varnish used on them should, when cured, be robust, water-resistant and flexible. Moreover, certain States are moving away from the use of paper as the substrate for bank notes, and so ideally any ink or varnish for such use should be useable on plastics as well as paper.
In addition, all the usual requirements of coating compositions intended for printing still apply - the coating composition should have a viscosity appropriate to the intended printing method, it should have acceptable toxicity, should ideally minimise the use of unsafe materials in the course of manufacture, even if they are not present in the finished product, and it should allow the use of a wide variety of pigments or dyes in order to maximise the possible colours for printing.
Also, it is preferred that the coating composition should be made available to the end user in as simple a form as possible, which, in practice, means in a single pack, with a storage stability measured in months, ideally at least 6 months, still better at least 12 months.
In order to meet the need to minimise the use of unsafe materials during manufacture, there is pressure to move away from the use of volatile organic solvents to aqueous-based compositions. In particular, N-methylpyrrolidone, which is a very common solvent often used in the preparation of polyurethane dispersions, has had for some years a question mark over its safety, and it would be highly desirable to avoid its use, whilst still maintaining the useful properties that it imparts to the finished product. Solvent free emulsion polymerised polymers contain free surface active agent, which then aggravates the requirement for water-resistance, since a composition applied in solution or dispersion in water may, unless it undergoes a fundamental change, also be easily removable in water or water-based fluids. Polyurethane dispersions are, in general, produced by the aqueous dispersion of pre- formed polymers, which are subsequently dispersed in water. In order to facilitate the aqueous dispersion step the isocyanate terminated prepolymer must have a workable viscosity/molecular weight. This viscosity regulation is achieved by a solvent diluent, commonly N-methylpyrrolidone, which remains in the final dispersion. The pre-polymer is then neutralised and transferred to water where spontaneous particle formation occurs. Chain extension is carried out at this stage, producing a high molecular weight polyurethane dispersion. No free surface active agent is usually required, which reduces re-dispersability on hot washing.
Several attempts have been made to meet these multitudinous and varied requirements. For example, WO 03/020835 describes a water-based screen printing ink composition having (a) an acrylic or urethane-acrylic copolymer emulsion; (b) a cross- linker; (c) optionally a catalyst; (d) optionally pigments; and (e) optionally additives, characterized in that said cross-linker comprises at least two different chemical functionalities within the same molecule, wherein a first of said functionalities is chosen such as to form a covalent link with said polymer prior to printing and a second of said functionalities is selected to effect cross-linking of said polymer to cure the printed ink
and that the acrylic or urethane-acrylic copolymer emulsion is selected from the group having self-cross-linking properties.
The unmodified acrylic or urethane-acrylic copolymer emulsions used in WO 03/020835 produce inadequate chemical and hot wash resistance. Reacting via a two step process with bi-functional silanes increases chemical and hot- wash resistance. However, these compositions hydrolyse with time in aqueous systems, reacting with acid groups in the polymer, after an induction period of up to two days. This reaction leads to an upward drift of pH, which may increase viscosity and reduce dispersion stability. The drift may be reduced, but not eliminated, by adjustment to near neutrality by the controlled addition of volatile organic amines. Organosilanes may also self condense with time making them unavailable for further reaction. A combination of these effects may compromise wet adhesion with time and particularly hot washing machine resistance, especially on polymer banknote type substrates. Hydrolysis also produces free alcohol ( methanol or ethanol), which is undesirable on Health and Safety grounds. The good chemical resistance of these acrylic copolymer systems depends on reaction with the bi-functional silanes, which may take up to a week with low temperature curing. This type of composition is sensitive to excessive mixing, which may initiate premature cross-linking, causing viscosity to rise and effecting machine properties.
These prior art compositions also cause a number of high speed rotary screen running problems, including in-line blocking and impaired distribution to the edge of the screen, producing reduced density at the edge. High speed rotary screen presses commonly have a 4-6 metre drying station at 120-160°C and a line speed up to 130m/minutes. Under these conditions, the dwell time is insufficient to dry the print by evaporation. Hence the main drying mechanism is by rapid absorption of the ink into a porous paper like substrate. Where, as with the prior art inks, the polymer properties are such as to prevent adequate penetration, sufficient "drying" may not be achieved, thus leading to the aforementioned problems.
The silanes also can react with pigments in competition with reaction with the polymer: this necessitates pigment pre- treatment, for example with a fiuorochemical surfactant. The increase in acid value also reduces base resistance.
We have now surprisingly found that these problems may be overcome and the above desiderata may be achieved by the use of specific polyurethanes, namely aliphatic polycarbonate polyurethanes and/or aliphatic polyester polycarbonate polyurethane copolymers, as the resin component of coating compositions. Dispersions of these polyurethanes have a broad distribution of particle sizes, including some very small particles, unlike the acrylic emulsion polymers. As a result, the polyurethane dispersions used in the present invention exhibit very unique film properties, especially in terms of mechanical properties ideally suited for this high performance surface coating application. In order to develop a film with the requisite mechanical and resistance properties the film particles must coalesce. The high molecular weigh polymer chains are contained within particles. Particles need to deform and coalesce to attain efficient interpenetration of the chains to result in a coherent film. This difficult condition is satisfied by the dispersion of the present invention due to the special dispersion and particle morphology of the polyurethanes used, hi addition, porous substrates may be physically interpenetrated by these very small broadly distributed dispersions, producing enhanced adhesion, hi the case of non-coated polymer films, solvation of the polymer by the cosolvent is required to produce interpenetration and adhesion.
Such polyurethanes are known. See, for example, US2007/0167565, US 5,349,041, US 5,334,690, EP 0837083, and EP 0969029. They have been used for a variety of purposes, including as automotive and other coatings. However, although US 5,334,690 suggests their use as printing inks, they have not been used for security printing, and we have discovered that, in order to be used successfully for such printing, they must have a particle size within a specific range and a certain minimum acid value. They should also be free from free isocyanate groups.
Thus, the present invention consists in a method of printing a value document, in which a printing ink or varnish comprising a dispersion of a resin is applied to the document, characterised in that the dispersion is an aqueous dispersion of a polycarbonate polyurethane and/or a polyether or polyester polycarbonate polyurethane copolymer having a particle size range from 10 to 400 nm and an acid value no greater than l0 mg KOH/g.
The value documents to which the present invention may be applied include bank notes, passports, gift tokens/vouchers, product authentication certificates, securities certificates etc., as well as any other form of document, whether printed on paper or an a plastics substrate, having similar security requirements to those of bank notes. However, it is thought that the invention will be of greatest value in relation to banknotes.
The polyurethanes of the present invention may be prepared by the reaction of a polyisocyanate with a diol or polyol. The preferred polyols are polycarbonate polyols, although other polyols such as polyether or polyester polyols may be included. The polycarbonate polyols may be produced via an ester interchange reaction or alcoholysis of diethyl carbonate or diphenyl carbonate with a polyol, preferably an alkylene diol. Examples of these diols are 1,4-butanidiol, 1,6-hexanidiol, or an alkylene ether diol e.g. triethylene glycol, glycerol or tripropylene glycol. Polyols with three or more hydroxyl groups, such as trimethylolpropane, glycerol and pentaerythritol can be incorporated for preparing polycarbonate polyols. Mixtures of polycarbonate polyols may be utilised and the polycarbonate backbone may be aromatic or aliphatic, but is preferably aliphatic in nature. It may also be linear or branched.
Examples of diisocyanate compounds include, but are not limited to, hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 4,4- dicyclohexylmethane diisocyanate (H12MDI), 2,24-trimethyl hexamethylene diisocyanate,2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), trimethylhexamethylene diisocyanate (TMDI), diphenylmethane diisocyanate (MDI), tetramethylene diisocyanate (TMXDI), and xylene diisocyanate (XDI). The above diisocyanate compounds may be used individually or in combination. Aliphatic diisocyanates are preferred to ensure low yellowing of the coating. Trimethylhexamine diisocyanate is an example of a preferred aliphatic isocyanate.
The neutralising agent for the aqueous dispersion stage should preferably be a low volatility organic amine, e.g. diethanolamine, diethylamine, triethylamine, morpholine or triethylamine. Triethylamine is an example of a preferred amine for this application.
Covalently cross-linkable functionalities may be built in within the polymer chains to further enhance mechanical and chemical resistance properties.
Suitable polycarbonate backboned polyurethane dispersions are available as Incorez W835/360, W835/364, W835/256 and W835/140 ex (Industrial Copolymers), U9160vp, U9152VP and U6150VP ex (Albedingk Boley).
The high molecular weight anionic polyurethane dispersion has polymer chains arranged with softer and harder segments. Softer segments arise from high molecular weight polyol components, while the harder segments arise from diisocyanates, low molecular weight diols and urethane urea bond sequences. The mixing of these segments yields specific film properties, which may be uniquely tailored to this coating application.
The polyurethanes of the present invention are preferably polydisperse, having an average particle size of from 40 to 100 nm, more preferably from 60 to 90nm and most preferably about 80 nm. The overall range of particle sizes is from 10 to 400 nm, more preferably from 20 to 200 nm.
It is particularly surprising that these relatively small particle sizes lead to improved adhesion of the composition to the substrate, since the prior art (see, for example, "Resins for Surface Coatings" (SITA), Vol. 2, p276-p277, which stresses the importance of the particle size being greater than the pore size, to prevent penetration and poor adhesion.
The acid value of the polyurethane is no greater than 10 mg KOH/g, preferably no greater than 9 and more preferably from 3 to 8.
It is highly desirable that the polyurethane dispersion should form a polymer film highly resistant to plasticisation and hydrolysis - if these happen, the wet tensile strength will be reduced and the film will be susceptible to chemical and physical attack. Polycarbonate polyurethanes are both tough and very hydrolytically stable, and so meet these requirements. As is well known in the art, by the incorporation of specialist functional groups, flexibility and elongation can be maintained. Other
polyols, such as polyether polyols, may be incorporated to increase hydrolytic stability still further.
The physical properties of the dried films of polyurethanes also pay a part in the present invention. A polyurethane film having a thickness of 50-100μm, dried at 22°C and tested after 7 days, preferably has an elongation at break of from 50 to 350%, more preferably from 150 to 300%. Such a film preferably has a Persoz hardness of 150 to 300 seconds, more preferably from 180 to 260 seconds. Such a film preferably has an ultimate tensile strength of from 10 to 50 MPa, more preferably from 13 to 30 MPa.
The amount of polyurethane may vary over a wide range as is well known in the art. However, in general, we prefer that it should comprise from 60 to 88%, more preferably from 60 to 75%, of the ink or varnish composition.
The remaining components of the printing ink or varnish are conventional and are well known to those skilled in the art. Examples of such other components are described in "Printing Ink Manual", fourth edition, Leach R. H. et al. (eds.), Van Nostrand Reinhold, Wokingham, (1988), the disclosure of which is incorporated herein by reference.
The polyurethane will normally be supplied as a dispersion, in which case a solvent may already be present. If there is no solvent or insufficient solvent, then a solvent should be added. Examples of suitable solvents include 2-(2-butoxyethoxy)- ethanol, tripropylene glycol monomethyl ether, N-ethylpyrrolidone and dipropylene glycol monomethyl ether. Preferred solvents should have boiling points greater than 200°C, flash point greater than 9O0C and evaporation rates 0.02-0.4, where butyl acetate = 100. The amount of solvent is preferably sufficient to reduce the minimum film- forming temperature of the ink or varnish to a value in the range from 0 to 400C. In general, the total solvent preferably comprises from 3 to 10, more preferably from 5 to 9%, of the ink or varnish composition. In the case of flat bed printing some of the added cosolvent may be replaced by a humectant at a level from 1 to 5%, to reduce drying on the screen. These humectants may be based on glycols, polyglycol, polyethers, acid amides, urea and polysaccharides (such as sorbitol), which may be used on their own or in combination. Examples of preferred humectants are Miraplast SCR-
47 from Bohner Chemie and diethylene glycol. Glycols like diethylene glycol are capable of lowering the minimum film forming temperature. Humectants, particularly the glycols, may also be added to improve low temperature and freeze/thaw stability.
The overall water content of the printing ink or varnish composition (including not only any added water, but also any water present in the other components of the composition) is preferably from 35 to 45% by weight, in order to achieve optimal printing without excessive substrate cockle.
For certain uses, in particular if the composition is to be printed by rotary screen printing, a defoamer may be incorporated. Preferred defoamers include polysiloxanes, polyether modified polydimethyl siloxane, polyether mixed with polyether siloxane and hydrophobic solids, such as Tego Foamex 805, 810, 812N, 822, 825 and 840 or Byk 011, 019, 024. Where used, the amount of defoamer is preferably from 0.5 to 2.0% of the composition.
Ancillary de-foaming and flow modifying agents may be included, for example:- polyoxyethylenated polyoxypropylene glycol, tertiary acetylenated glycols (e.g.
Surfynol 104, 104H, 420 - ex Air products), polyoxyethylenated alcohol ethoxylates (e.g. Tego Wet 500) and silicone polymers (e.g. Tego Wet 270, Coat O SiI MP200). Where used, the amount is preferably in the range from 0.1 to 2%, more preferably from 0.1 to 0.5% by weight of the composition.
It may also be necessary to include a thickener, depending on the intended printing technique. Such thickeners and the amounts thereof are well known to those skilled in the art. However in the case of compositions containing iridescent pigments of large particle size and high density, the thickener or blend must be carefully selected to resist settlement under gravitational stress, while having delayed structural recovery to allow particle alignment after printing. Examples of suitable thickeners include Bentone DE, Reolate 125 ex Elementis, Acrysol RM-8W, Byk 420E, and Byk 425 ex Bky Chemie. It was found that the blend that was most preferred should include modified urea and or polyurethane urea at 0.1 to 0.6 %. These are available as Byk 420E and Byk 425.
In the case of an ink, the composition should include a pigment, which may be chosen from any of those known for use in printing inks. The amount of pigment is preferably from 15 to 19% of the composition for screen printing applications, hi general, we prefer that the weight ratio of pigment to binder (including the polyurethane and any other binder present) should be from 1 : 1.1 to 1 : 1.5, in order to optimise abrasion resistance and control finish.
For certain types of pigment used in the printing of value documents, especially iridescent pigments, a pigment dispersant is important to minimise settlement and improve re-dispersion. The selected dispersant is preferably an amine neutralised polyacrylate, which is particularly suited because, on drying, amine is lost and film water resistance is not compromised. Other dispersants based on chemistries such as styrene maleic anhydride (e.g. Disperse Ayd W22) may be used.
hi order to improve hot washing machine resistance, it is also desirable to include a polycarbodiimide in the composition. Examples of polycarbodiimides are given, for example, in US 5,258,481 and 5,047,588, the disclosure of which is incorporated herein by reference. The emulsion grades of polycarbodiimides are to be preferred for maximum shelf life. The preferred polycarbodiimide is Carbodelite (ex Nisshinbo Industries). Where a polycarbodiimide is used, the amount is preferably from 1.0 to 2.5% of the composition.
Other conventional additives, such as those identified in "Printing Ink Manual", may also be included in the composition, if desired. It is, of course, well understood that any additives used must not interfere with coating overprint ability, blocking on the reel and sticking on subsequent printing operations.
The compositions of the present invention may be used in any printing technique for printing on a substrate, but are especially suitable for rotary screen printing.
The compositions of the present invention are only able to penetrate the surface of the substrate, and thus adhere to it, if they are of appropriate coating viscosity and if their surface energy is low enough to achieve adequate wetting. This is a precondition for the very fine polyurethane particles penetrating the substrate surface layer. The extent of the penetration is dependent on the surface treatment and the internal substrate
structure.. Surface coatings, paper compression and internal binders may reduce penetration, in which case adhesion may be compromised. Alteration of co-solvent, wetting and other dispersion additives may alleviate the problem, as is well known in the art. Polymer based banknote substrates are generally coated with print receptive matt layers, with unprinted areas remaining as clear windows. These coatings are commonly approximately 5-7μm in thickness with a surface tension of 44mN/m. The compositions of the present invention are capable of wetting and penetrating the surface coated layer, producing good adhesion.
As is well known for the printing of banknotes, the printing ink or varnish should be free from compounds which fluoresce under ultraviolet, should not yellow when heated to 150°C, should meet health and safety criteria (lack of irritancy, toxicity and sensitisation), and should have a flash point greater than 1000C.
The invention also provides value documents, especially bank notes, printed by the method of the present invention.
The invention is further illustrated by the following non- limiting Examples.
EXAMPLE 1
The following components were blended together until homogeneous, with no lumps, to form a thickener blend 1 (amounts are parts by weight):
Acrysol RM-8W 45.8
Collacral VAL 22.9
Byk 425 8.3
De-ionized water 22.9
69.3% by weight of Incorez W835/360 (an aliphatic polyester polycarbonate polyurethane) were then charged into a container, and 3.0% by weight of 2-(2- butoxyethoxy)ethanol (a cosolvent) were added and mixed. The following components were then added in the following order, mixing all the time until there were no bits or lumps:
Tego Disperse 750W 4.0% (Dispersant)
Thickener blend 1 1.5%
Tego Foamex 805 1.6% (Defoamer)
Lustrapak Yellow fine grade 18.0% (Security pigment)
Coat O SiI MP200 0.6% (Polymeric silane)
Carbodelite E-O2 2.0% [multifunctional polycarbodiimide (40% dispersion)]
The mixture was immediately filtered twice, each time through a 100 micron filter, after which it was filled into containers, to give a rotary screen ink, acid value 8mg. KOH/g, pH 9, particle size 30-200 nm.
EXAMPLE 2
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 20mg. KOH/g, pH 8, particle size 50-200 nm:
U9160VP 64.9% (Aliphatic polyester polycarbonate P.U.D.)
2-(2-Butoxyethoxy)ethanol 6.3%
Tego Disperse 750W 4.0%
Thickener blend 1 1.6%
Tego Foamex 805 1.2%
Lustrapak Yellow fine grade 20.0%
Carbodelite E-O2 2.0%.
EXAMPLE 3 (Comparative)
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, pH7-8, particle size 0.5-1.5 microns.
Ubatol E95435 65.1% (Acrylic self-crosslinking)
Aquacer 526 8.0% (Ethylene-vinyl acetate dispersion)
Tego Disperse 750W 5.0%
Tego Foamex 810 1.2% (Defoamer)
Thickener blend 2 0.7% (see below)
Lustrapak yellow fine grade 20.0%
Thickener blend 2 was prepared by mixing the following components using a similar procedure to that described in Example 1.
Acrysol RM-8W 50%
Collacral VAL 25%
De-ionised water 25%
EXAMPLE 4 (Comparative)
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 20mg. KOH/g, pH 7-8, particle size 50-250 nm.
U938 VP 73.1% (Aliphatic polyester polyurethane dispersion)
Tego Disperse 750W 4.0%
Thickener blend 2 0.8%
Tego Foamex 805 1.2%
Wetlink 78 0.9% (bi-functional organosilane)
Lustrapak yellow fine grade 20.0%
Example 4 contains N-methylpyrrolidone in the polyurethane dispersion, and is also a potential sensitizer because of the presence of the bi-functional organosilane.
EXAMPLE 5
Following the procedure described in Example 1, the following components were mixed to form a flat-bed screen ink, acid value 8.0 mg KOH/g, pH 8.5-9.0, particle size 20-100nm.
Incorez W835/360 67.0%
Diethylene glycol 4.0%
Tego Disperse 750W 3.0%
Thickener blend 1 1.8%
Tego Foamex 805 1.6%
Lustrapak fine grade yellow 20.0%
Coat O SiI MP200 0.6
Carbodelite EO-2 2.0%
EXAMPLE 6
Following the procedure described in Example 1, the following components were mixed to form a flat-bed screen ink, acid value 8.0 mg. KOH/g, pH8.5-9.0.
Incorez W835/360 62.0%
U9160 VP 7.3%
2-(2-Butoxyethoxy)ethanol 3.0%
Tego Disperse 750W 4.0%
Thickener blend 1 1.5%
Tego Foamex 805 1.6%
Lustrapak yellow fine grade 18.0%
Coat O SiI MP200 0.6%
Carbodelite E-O3A 2.0%
EXAMPLE 7
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, pH 9, particle size 40- lOOnm.
Incorez W835/360 53.3%
APU 10140 VP 16.8%
Tripropylene glycol monomethyl ether 4.4%
Tego Disperse 750W 4.0%
Thickener blend 1 1.1%
Tego Foamex 805 1.8%
Lustrapak yellow 18.0%
Carbodelite VO2-L2 1.6%
EXAMPLE 8
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, , pH 9, particle size 40- lOOnm.
Incorez W835/360 70.4%
Aquacer 526 3.0%
Tego Disperse 750 W 4.0%
Thickener blend 1 1.4%
Tego Foamex 805 1.4%
Lustrapak yellow 18.0%
Carbodelite EO-3A 2.0%
EXAMPLE 9
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, , pH 9, particle size 40- lOOnm.
Incorez W835/360 54.6%
Incorez W835/256 14.6% (Aliphatic polycarbonate polyurethane dispersion)
Tego Disperse 750W 4.0%
Tripropylene glycol monomethyl ether 2.0%
Thickener blend 1 1.5%
Tego Foamex 805 1.4%
Lustrapak yellow 20.0%
Carbodelite EO-2 2.0%
EXAMPLE 10
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8mg KOH/g, , pH 9, particle size 40- lOOnm.
Incorez W835/360 51.6%
U9800 VP 16.0% (Aliphatic polyester polyurethane dispersion)
Tego Disperse 750 W 4.0%
2-(2-Butoxyethoxy)ethanol 2.5%
Thickener blend 1 1.5%
Tego Foamex 805 1.8%
Lustrapak yellow 20.0%
Coat O SiI MP200 0.6%
Carbodelite EO-2 2.0%
EXAMPLE 11
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8-9 mg KOH/g, pH 8-9, particle size 40-100nm.
Incorez W835/360 48.8%
Incorez W835/364 21.0% (Aliphatic polycarbonate polyurethane dispersion)
Tego Disperse 750 W 3.0%
2-(2-Butoxyethoxy)ethanol 3.0%
Thickener blend 1 1.5%
Tego Foamex 805 1.4%
Lustrapak yellow 18.0%
Coat O SiI MP200 0.6%
Carbodelite EO-2 2.0%
EXAMPLE 12
Following the procedure described in Example 1, the following components were mixed to form a rotary screen ink, acid value 8-9 mg KOH/g, pH 8-9, particle size 40-lOOnm.
Incorez W835/360 54.6%
Incorez W835/256 14.0% (Aliphatic polycarbonate polyurethane dispersion)
Tego Disperse 750W 4.0%
Tripropylene glycol monomethyl ether 2.0%
Thickener blend 1 1.4%
Tego Foamex 805 1.4%
Lustrapak yellow 20.0%
Coat O SiI MP200 0.6%
Carbodelite VO2-L2 2.0%.
MATERIALS
The materials used were obtained as follows:
Incorez W835/360 Industrial Copolymers Ltd.
U938 VP Albedingk Boley.
U9160 VP Albedingk Boley.
APU 10140 Albedingk Boley
Neocryl XKl 1 NeoResins.
Neo Pac E- 125 NeoResins.
Ubatol E95435 Cray Valley
Coat O SiI MP200 GE Silicones.
Coat O SiI 1770 GE Silicones
Wetlink 78 GE Silicones.
Carbodelite E-O2 , E-O3A. Nisshinbo Industries.
Byk 420,425,024, 025. Byk Chemie.
Aquacer 526 Byk Chemie.
Lustrapak yellow Merck.
Rheolate 276 Elementis
Acrysol RM-8W. Rohm & Haas
Collacral VAL. BASF
Jonwax 22. BASF
TESTS
Machine Tests (Physical)
All prints were produced on E.C.B. (European Central Bank) specified Banknote paper. The printing was carried out on a Rotary screen Stork machine, incorporating hot air drying. The rotary screen produced feature was converted to a complete value document (Banknote). The Physical tests were conducted according to E.C.B.
specifications. The wet and dry Crumple test ( 8x ), and wet and dry Abrasion test have been correlated with feature lifespan. The tests include a 90°C hot washing machine test. All test scores are marked on a scale of 0-4. The minimum specification for the tests shown is 2. All prints were also subjected to a vibrating balls Abrasion test and tested for Hot ironing resistance. All the examples included passed both tests. The results are shown in Table 1.
Table 1
The Rotary screen printed value documents (Banknotes ), were also subjected to the full E.C.B. battery of 16 Chemical tests. All the Examples quoted passed the tests at least to the minimum standard.
Stability Tests
The stability of ink systems were assessed via storage at room temperature and at 4O0C in tightly closed glass containers. Viscosity measurements were made to monitor thickening and changes in structure. The inks were printed and tested for hot washing machine resistance as a function of storage time. The hot washing machine test is very sensitive to changes due to aging of the ink system. Solvent resistance tests based on number of rubs have been used in the past to assess ageing of ink systems. These measurements were found not to correlate with hot washing tests.
A score of 4 out of 4 on the test represents no removal of the printed security feature and 0 represents complete removal. The test is subject to some variation and is usually repeated on 5 samples and the results averaged out. The structural changes in the inks were assessed using a DIN 4 flow cup at 220C and a Bohlin CS Rheometer using cup and bob geometry. Storage tests were suspended if the times on the flow cup had increased by more than 5 seconds. Only samples that passed this assessment were hot washing machine tested. It is to be noted that samples settle to varying degree and they must be remixed until homogeneous before viscosity measurement or printing. The results are shown in Table 2.
Table 2
Laboratory Chemical & Physical Tests.
Sample prints were prepared by Screen printing (77T mesh), onto a range of banknote type papers. Prints were also produced via coating with a no 3 bar. All the prints were thoroughly hot air dried. The prints were left for 8 hours and tested with solvents applied with cotton buds. The number of low pressure double rubs was recorded. The prints were also cross-hatch tape tested (Tessa tape). The results were recorded on a 0-4 scale, with 4 representing no removal.
Hot washing machine tests were conducted according to E.C.B. specification.
The results are shown in Tables 3 to 6.
Table 3
Claims
1. A method of printing a value document, in which a printing ink or varnish comprising a dispersion of a resin is applied to the document, characterised in that the dispersion is an aqueous dispersion of a polycarbonate polyurethane and/or a polyether or polyester polycarbonate polyurethane copolymer having a particle size range from 10 to 400 nm and an acid value no greater than 10 mg KOH/g.
2. A method according to Claim 1, in which the polycarbonate polyurethane and/or polyether or polyester polycarbonate polyurethane copolymer is an aliphatic polycarbonate polyurethane and/or polyether or polyester polycarbonate polyurethane copolymer.
3. A method according to Claim 1 or Claim 2, in which the polyurethane is polydisperse, having an average particle size of from 40 to 100 nm.
4. A method according to Claim 3, in which the particle size is from 60 to 90nm.
5. A method according to Claim 4, in which the particle size is about 80 nm.
6. A method according to any one of the preceding Claims, in which the overall range of particle sizes is from 20 to 200 nm.
7. A method according to any one of the preceding Claims, in which the ink or varnish comprises a solvent having a boiling point greater than 200°C.
8. A method according to any one of the preceding Claims, in which the value document is a banknote.
9. A method of printing a value document, in which a printing ink or varnish is applied to the document, the ink or varnish comprising:
from 60 to 88% by weight of an aqueous dispersion of a polycarbonate polyurethane and/or a polyether or polyester polycarbonate polyurethane copolymer having a particle size range from 10 to 400 nm and an acid value no greater than 10 mg KOH/g;
optionally from 0.5 to 2.0% of a defoamer; from 3 to 10% of a solvent; and
optionally from 15 to 19% of a pigment.
10. A value document printed by a method according to any one of the preceding Claims and dried.
11. A value document according to Claim 10, which is a banknote.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CA2714000A CA2714000A1 (en) | 2008-02-05 | 2009-02-05 | Printing ink for value or security documents |
EP09707324A EP2245100B1 (en) | 2008-02-05 | 2009-02-05 | Printing ink for value or security documents |
US12/866,144 US8329777B2 (en) | 2008-02-05 | 2009-02-05 | Printing ink for value or security documents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB0802110A GB2457239A (en) | 2008-02-05 | 2008-02-05 | Printing ink for value or security documents |
GB0802110.7 | 2008-02-05 |
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WO2009098456A1 true WO2009098456A1 (en) | 2009-08-13 |
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PCT/GB2009/000315 WO2009098456A1 (en) | 2008-02-05 | 2009-02-05 | Printing ink for value or security documents |
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US (1) | US8329777B2 (en) |
EP (1) | EP2245100B1 (en) |
CA (1) | CA2714000A1 (en) |
GB (1) | GB2457239A (en) |
WO (1) | WO2009098456A1 (en) |
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US20130065467A1 (en) * | 2011-09-10 | 2013-03-14 | Sun Chemical Corporation | Substrate Printed with a Water-Based Urethane Printing Ink with Improved Performance Properties |
EP2948249A1 (en) | 2013-01-22 | 2015-12-02 | University of Washington through its Center for Commercialization | Sequential delivery of fluid volumes and associated devices, systems and methods |
US10213954B2 (en) * | 2016-02-19 | 2019-02-26 | The Boeing Company | Natural path forming for composite material |
AU2017100680B4 (en) * | 2017-06-08 | 2018-01-18 | Ccl Secure Pty Ltd | Methods of simulating wear and evaluating wear-resistance of a functionalised substrate for preparation of or use as a security document |
US10961406B2 (en) | 2018-02-12 | 2021-03-30 | Sun Chemical Corporation | Smear resistant ink composition |
JP7041393B2 (en) * | 2018-06-05 | 2022-03-24 | 株式会社リコー | Resin emulsion for water-based ink, ink for water-based inkjet, recording device, and recording method |
DE102019123227A1 (en) * | 2019-08-29 | 2021-03-04 | Bundesdruckerei Gmbh | Procedure for testing the durability of data carriers and security documents |
CN110528320A (en) * | 2019-09-12 | 2019-12-03 | 中山市中益油墨涂料有限公司 | A kind of aqueous alkaline-resisting gloss oil and preparation method thereof on trade mark paper |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0805172A2 (en) * | 1996-04-30 | 1997-11-05 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Polycarbodiimide compound, production process thereof, resin composition, and treatment method of article |
WO2003020835A1 (en) * | 2001-08-28 | 2003-03-13 | Sicpa Holding S.A. | Water-based screen printing ink |
US20040242726A1 (en) * | 2002-05-16 | 2004-12-02 | Minoru Waki | Pigment dispersion and ink composition for ink-jet |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2215304C (en) * | 1995-03-13 | 2004-06-22 | Portals Limited | Security paper |
DE10251797A1 (en) * | 2002-11-07 | 2004-05-19 | Bayer Ag | Polyurethane resin with a high carbonate group content |
-
2008
- 2008-02-05 GB GB0802110A patent/GB2457239A/en not_active Withdrawn
-
2009
- 2009-02-05 US US12/866,144 patent/US8329777B2/en active Active
- 2009-02-05 EP EP09707324A patent/EP2245100B1/en active Active
- 2009-02-05 CA CA2714000A patent/CA2714000A1/en not_active Abandoned
- 2009-02-05 WO PCT/GB2009/000315 patent/WO2009098456A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0805172A2 (en) * | 1996-04-30 | 1997-11-05 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Polycarbodiimide compound, production process thereof, resin composition, and treatment method of article |
WO2003020835A1 (en) * | 2001-08-28 | 2003-03-13 | Sicpa Holding S.A. | Water-based screen printing ink |
US20040242726A1 (en) * | 2002-05-16 | 2004-12-02 | Minoru Waki | Pigment dispersion and ink composition for ink-jet |
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CA2714000A1 (en) | 2009-08-13 |
EP2245100A1 (en) | 2010-11-03 |
US8329777B2 (en) | 2012-12-11 |
US20110025038A1 (en) | 2011-02-03 |
GB2457239A (en) | 2009-08-12 |
GB0802110D0 (en) | 2008-03-12 |
EP2245100B1 (en) | 2012-09-05 |
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