WO2004039913A2 - Process for incorporation of uv-luminescent compounds in polymeric materials - Google Patents
Process for incorporation of uv-luminescent compounds in polymeric materials Download PDFInfo
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- WO2004039913A2 WO2004039913A2 PCT/EP2003/011638 EP0311638W WO2004039913A2 WO 2004039913 A2 WO2004039913 A2 WO 2004039913A2 EP 0311638 W EP0311638 W EP 0311638W WO 2004039913 A2 WO2004039913 A2 WO 2004039913A2
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- process according
- formula
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims description 32
- 239000000463 material Substances 0.000 title claims description 23
- 238000010348 incorporation Methods 0.000 title description 9
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- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 41
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 41
- 239000003446 ligand Substances 0.000 claims abstract description 20
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- 239000004753 textile Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- -1 amino, pyrrolidino Chemical group 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 17
- 239000004033 plastic Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 10
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- 238000009472 formulation Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
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- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000003247 decreasing effect Effects 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000013522 chelant Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
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- 238000004020 luminiscence type Methods 0.000 description 6
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
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- 125000001424 substituent group Chemical group 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
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- 229920000742 Cotton Polymers 0.000 description 3
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- RZCYUOWKJNUVBF-KAMYIIQDSA-M [O-]/C(/c1ccccc1)=C\C(c1ccccc1)=O Chemical compound [O-]/C(/c1ccccc1)=C\C(c1ccccc1)=O RZCYUOWKJNUVBF-KAMYIIQDSA-M 0.000 description 2
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- AZYTZQYCOBXDGY-UHFFFAOYSA-N 2-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=CC=N1 AZYTZQYCOBXDGY-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- CRQJERFKOCCFPE-UHFFFAOYSA-N 5-methyl-1,3-bis(piperidin-1-ylmethyl)-1,3,5-triazinane-2-thione Chemical compound S=C1N(CN2CCCCC2)CN(C)CN1CN1CCCCC1 CRQJERFKOCCFPE-UHFFFAOYSA-N 0.000 description 1
- 229920006045 Akulon® Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical class C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920005373 Plexiglas® 6N Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920003825 Ultramid® B3K Polymers 0.000 description 1
- UGHMGUXSEYFBLC-DAXSKMNVSA-M [O-]/C(/C(F)(F)F)=C\C(c1ccc[s]1)=O Chemical compound [O-]/C(/C(F)(F)F)=C\C(c1ccc[s]1)=O UGHMGUXSEYFBLC-DAXSKMNVSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical class 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical class C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical class 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/387—Special inks absorbing or reflecting ultraviolet light
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a process for the preparation of luminescent textile fibres characterized in that the fibres are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.
Description
Process for Incorporation of UV-luminescent Compounds in Polymeric Materials
The present invention relates to a process for the preparation of UV luminescent polymeric materials and their uses.
There is a need for furnishing textiles with covert effects, which may act as security markings, as special effects or as decorations that only become visible under UV irradiation.
It is therefore an object of the present invention to provide a dyeing composition comprising a substance which is invisible to the unaided eye but yields a strong luminescence under UV exposure and which composition can be used for all conventional dyeing applications of polymeric materials including textiles such as wool, silk, cellulosic materials, natural and synthetic fibres as well as for the mass dyeing of polymeric materials including those used in textile and plastic applications.
The invention relates to a process for the preparation of luminescent polymeric fibres characterised in that the fibres are treated with a composition comprising
(a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one UV absorbing group and
(b) one or more solvents.
Preferably, component (a) is a compound of formula I
Lm-Ln3+(Ch-)n (I), wherein Ln represents a lanthanide,
Ch" is a negatively charged ligand containing at least one UV absorbing double bond, n denotes 3 or 4, m denotes a number from 0 to 4, in case n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4, m denotes 1 and L is a single-charged cation.
More preferably, component (a) is a compound of formula II, III or IV
Lm-LnJ+[R Oln (IV),
wherein Ln represents a lanthanide, n denotes 3 or 4, m denotes a number from 0 to 4 in case n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4, m denotes 1 and
L is a single-charged cation,
R2, is hydrogen or C C6alkyl, and
RT and R3 are each independently of the other hydrogen, d-Cβalkyl, CF3l C5-C24aryl or
C -C2 heteroaryl.
The compounds of formula I, II, III or IV can basically contain any neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand such as, for example, unsubstituted or substituted pyridine, pyrazine, piperidine, quinoline, aniline, bipyridine, phenanthroline, terpyridine, imidazole, benzimidazole, bisimidazole, bisbenzimidazole, pyrimidine, bipyrimidine, naphthyridine, alkylamine, dialkylamine, trialkylamine, alkylene polyamine, dioxane, dimethylsulfoxide, dimethylformamide, phosphine-oxide derivative (trialkyl or triaryl), triazine, bistriazine, oxazole, bisoxazole, oxazoline, bisoxazoline and substituted derivatives thereof and all relevant (poly)N-oxide derivatives of above cited ligands.
Particularly preferred are compounds of formula I, II, III or IV wherein n denotes 3 and L is a nitrogen-containing ligand.
Since L can be a polychelating ligand, like for example 4,4'-bipyridyl, the compounds of formula I, II, III and IV include multimetallic chelates, such as for example the compounds of
formula XIII and XIV, containing two M -(diketone)3 or M -(carboxylate)3 units connected via a bidentate ligand:
When n denotes 4, L as single-charged cation can be basically any metal cation (e.g. Li\ K+, Na+), unsubstituted or substituted ammonium (e.g. NH4 +, polyalkylammonium) or any protonated or alkylated monodentate or polydentate ligand as described above.
Preferred positively charged ligands are piperidinium, ammonium, alkylammonium, dialkylammonium and, in particular, trialkylammonium.
Triethylammonium is especially preferred.
Particularly preferred are compounds of formula I, II, 111 or IV wherein L is a compound of formulae V to XII
Alkyl groups as substituents R^ to R7 can be straight chain or branched. Examples which may be mentioned are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl and isohexyl.
Alkoxy groups as substituents R to R6 can be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.
Examples of C5-C24aryl groups are phenyl, tolyl, mesityl, isityl, diphenyl, naphthyl and anthryl. Phenyl is preferred.
Heteroaryl group preferably contain 4 or 5 C atoms and one or two heteroatoms selected from O, S and N. Examples are pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or chinolyl.
Aralkyl groups as substituents R to R7 can be, for example, benzyl, 2-phenylethyl, tolylmethyl, mesitylmethyl and 4-chlorophenylmethyl.
Suitable dialkylamino groups are, for example, diethylamino, diisopropylamino, di-n-propylamino, N-methyl-N-ethylamino and, in particular, dimethylamino or pyrrolidino.
Suitable cyclic amino groups are pyrrolidino and piperidino.
Halogen atoms as substituents R4 to Re are preferably fluorine, chlorine or bromine, but in particular chlorine.
Preferred compositions according to the invention contain as component (a) a compound of formula II wherein L is a compound of formula V, VI, VII, VIII, IX, X, XI or XII wherein P , R5 and R6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N+(R7)3.wherein R7 is CrC6alkyl.
Preferred components (a) are compounds of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm or Nd.
Furthermore, compounds of formula II and III are preferred, wherein Ri and R3 are methyl, t-butyl, n-pentyl or phenyl.
R2 in formula II is preferably hydrogen.
Particularly preferred as component (a) are the compounds of formula XIII to CVI:
C(CH, , )3 (XVI),
CH 3 ) (XVIII),
(XXVlll),
Tb (XXXI), Tb (XXXll),
Tb* (XXXIll), Tb (XXXIV),
(XXXVI),
(XXXVlll),
Eu ( (H3C)3<
Eu
(XXXXII),
Dy3+
(XXXXIV),
Dy3+
Dy (XXXXVI),
(XXXXVI 11),
Nd3+ ( HH,3C
Nd 3+ ( (H3C)3 <
Some preferred derivatives of structures of type II and III, derived from the above drawn preferred structures of type I, are compiled in the table below:
DMAP: 4-dimethylaminopyridine
Further suitable lanthanide chelates may contain
• pyridine, aminopyridine, pyrrolidinopyridine, methylpyridine, methoxypyridine, pyridine-N-oxide, bipyridine, phenanthroline, imidazole or any other derived or similar N, O or S containing mono- or polydentate ligand in place of DMAP piperidinium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, pyridinium or any other similar N containing protonated species in place of Et3NH+
For certain applications it is recommendable to use a combination of different lanthanides, for example Eu and Tb. Such a mixture increases the degree of security of the hidden colourations, the sophistication of the security level and multiplies the coding possibilities.
The compounds of formula I, II, III and IV are known, for instance from WO 96/20942 and from CR. Hurt et al., Nature 212, 179-180 (1966), or can be prepared by methods known per se. For example, a ligand such as acetylacetone, benzoylacetone, dibenzoylmethane,
dipivaloylmethane, salicylic acid, valeric acid or caproic acid can be reacted under suitable conditions with a rare earth metal halide such as a lanthanide trichloride to produce the rare earth metal chelate. Further reaction with the monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand L thus yielding the rare earth metal chelate compounds of formula I, II, III and IV.
The luminescent lanthanide chelate can be applied as a powder, as a solution or as a dispersion.
Accordingly, component (b) may be water, an organic solvent, a mixture of two or more organic solvents or a mixture of water and one or more organic solvents.
Preferably, component (b) is water, one or more water-miscible organic solvents or a mixture of water and one or more water-miscible organic solvents.
Suitable organic solvents include alcohols, glycols, ether alcohols, sulfoxides, amides, amines, heterocyclic solvents, ketones, ethers, esters, nitriles and aliphatic, cycloaliphatic and aromatic hydrocarbons.
Examples of suitable organic solvents are methanol, ethanol, n-propanol, isopropanol, n-butanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monoethylether, polyethyleneglycol dimethyether, ethoxybutanol, 2-butoxyethanol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, 2-butanone, diethylether, di-n-propylether, tetrahydrofurane (THF), ethyl acetate, ethyl propionate, acetonitrile, pyridine, n-pentane, n-hexane, cyclohexane, benzene and toluene.
The water-miscible organic solvent is preferably an aliphatic alcohol, etheralcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatic sulfoxide.
Particularly preferred water-miscible organic solvents are ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofurane (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile, polyethyleneglycol dimethyether and dimethylsulfoxide (DMSO).
The compositions according to the invention may, in addition to components (a) and (b), comprise one ore more colorants (c).
Suitable colorants are the well-known pigments and dyes including mixtures of different pigments and dyes.
In the compositions according to the present invention the amounts of components (a) and (b) and where appropriate (c) and/or further ingredients (d) can vary within wide ranges.
For a mass-dyeing process, the compositions according to the present invention consist of component (a). Optionally, further ingredients (c) and/or (d) may also be added together with (a) in order to give simultaneous supplementary propertie(s) to the polymeric material in addition to the UV-luminescence.
For a dyeing process, preferred compositions contain 0.01 to 20.0 %, more preferably 0.05 to 10 % and in particular 0.1 to 5.0 %, by weight of component (a) and 80.0 to 99.99 %, more preferably 90.0 to 99.95 % and in particular 95.0 to 99.9 %, by weight of component (b), based on the total amount of components (a) + (b).
The amount of component (c) depends on the type of substrate as well as on the specific pigment or dye. Advantageous amounts will generally be 0.01% to 15% by weight and especially 0.1% to 10% by weight, of colorant based on the weight of fibre.
Further ingredients (d) which may be present in the compositions according to the invention are e.g. optical brighteners, biocides, bactericides, fungicides insecticides and fragrance.
The compositions containing at least one lanthanide chelate can be prepared by any suitable method known to those of ordinary skill in the art. For example, the components of the composition can be combined and mixed in a suitable mixer or blender.
The compositions according to the invention are useful for impregnating manufactured natural, artificial and especially synthetic hydrophobic materials, especially textile materials.
Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic fiber materials can likewise be impregnated with the formulations of the invention.
Useful manufactured natural polymer textile materials are especially wool, cotton, silk, cellulose acetate and cellulose triacetate.
Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane; polycarbonates, for example those formed from α,α-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; or fibres based on polyvinyl chloride or polyamide.
The formulations according to the invention are applied to the textile materials according to known dyeing processes. For example, polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatures between 80 and 140°C, preferably between 120 and 135°C. Cellulose acetate is preferably dyed at between 60 to 85°C and cellulose triacetate at up to 115°C.
The formulations used according to the invention are useful for dyeing by the thermosol, exhaust and continuous processes and for printing processes. The exhaust process is preferred. The liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be chosen to be within a wide range, for example in the range from 4:1 to 100:1 , but it preferably is between 6:1 to 25:1.
The textile material mentioned may be present in the various processing forms, for example as a fibre, yarn or web or as a woven or loop-formingly knitted fabric.
The luminescent lanthanide chelates of the invention are likewise useful for mass-dyeing of plastics.
Accordingly, the invention further relates to a process for the preparation of luminescent plastics characterized in that the plastics material is extruded in the presence of 0.01 - 10.0
% by weight, based on the amount of plastics material, of a compound of formula I, II, III or IV.
Plastics useful for mass dyeing include for example dyeable high molecular weight organic materials (polymers) having a dielectric constant > 2.5, especially polyester, polycarbonate (PC), polystyrene (PS), polypropylene (PP), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadiene/styrene (ABS). Preference is given to polyester and polyamide. Particular preference is given to linear aromatic polyesters obtainable by polycondensation of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane, for example polyethylene terephthalate (PET) or polybutylene terephthalate (PBTP); polycarbonates, for example polycarbonates formed from α,α-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; polymers based on polyvinyl chloride or polyamide, for example nylon 6 or nylon 6.6, polystyrene (PS) or polypropylene (PP).
Very particular preference is given to plastics based on linear aromatic polyesters, for example those formed from terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane, polymethyl methacrylate (PMMA), polypropylene (PP) or polystyrene (PS).
The plastics are dyed for example by mixing the luminescent lanthanide chelate according to component (a) into these substrates using roll mills or mixing or grinding apparatus whereby the lanthanide chelates are dissolved or finely dispersed in the plastic. The plastic with the admixed dyes is then processed in a conventional manner, for example by calendering, pressing, extrusion, spread coating, spinning, casting or injection moulding, whereby the dyed material acquires its ultimate shape. The mixing of the components can also be effected directly prior to the actual processing step, for example by continuously metering solid, for example pulverulent, lanthanide chelates and a granulated or pulverulent plastic and also optionally additional substances such as for example additives simultaneously directly into the inlet zone of an extruder where the mixing-in takes place just prior to the processing. In general, however, prior mixing of the lanthanide chelates into the plastic is preferable, since more uniformly impregnated substrates are obtainable.
The invention further relates to luminescent textile fibre and to luminescent plastic prepared by the process described above.
The present invention makes it possible to incorporate colourless or coloured hidden marks into various colourless, white, pale coloured or dark coloured substrates, which can be revealed under UV exposure.
The claimed process is particularly useful for the manufacture of security fibres or security threads that can be applied to fiduciary documents or other materials. Security fibres are incorporated in fiduciary documents or other materials for the purpose of ensuring identification, an authentication, a protection against forgery, imitation or falsification. Security threads are continuous threads or strips of film introduced into fiduciary documents for the same purpose as security fibres.
The expression "fiduciary documents" denotes papers, such as papers for bank notes, cheques, shares , bills, stamps, official documents, identity cards, passports, record books, notes, tickets, vouchers, bulletins, accounting books as well as credit, payment, access or multifunctional cards, and similar documents which necessarily involve a high degree of security.
The manufacture of security fibres or security threads can be accomplished by known methods as described, for example, in U.S. Patents Nos. 4,655,788, 5,759,349 and 6,045,656, EP-A 185 396 and EP-A 1 013 824.
Incorporation of the lanthanide chelate compound can be carried out by conventional dyeing or printing processes.
Suitable fibres for the claimed process can be obtained from wood or vegetable pulp, cellulose pulp, cotton, linen or synthetic fibres.
Preferably, paper fibres or synthetic fibres are used.
In a particularly preferred embodiment the process according to claim 1 is used for the preparation of anti-counterfeit documents, cards, cheques or banknotes.
The compositions according to the invention distinguish from analogous prior art compositions by outstanding luminescence quantum yield, long-lasting luminescence and high luminescence intensity.
The following Examples illustrate the invention.
Ink Composition A:
Concentrate of compound XVII in 1 ,2-propylene glycol
1 g of compound VIII is dissolved in 99 g of 1 ,2-propyleneglycol under heating at 100°C for 1 hour. The clear yellow solution is allowed to cool down and after filtration (clarification) provides the stable Ink Composition A which exhibits an intense red luminescence under UV light. This concentrate can be further used in either solvent based or aqueous based conventional or high-tech (ink-jet) printing formulations for paper, textile, leather, wood, plastic or other compatible substrates.
Example 1 :
The impregnation of a cellulosic bobbin (0.75kg cotton thread 40tex) is performed at 35°C for 20 min in an alternated circulation dyeing apparatus (Callebault de Blicquy) (3 min cycle) with a liquour ratio of 1 to10. The liquour contains 4.5% of the compound of formula XVII
in 2-butoxy-ethanol.
After treatment, centrifugation and air-drying of the bobbin, strong red-orange fluorescence is observed under UV light.
Example 2:
The impregnation of a silk thread (10g) is performed at 25°C for 10-60 min in the same liquour and liquour ratio to textile material as described in Example 1. After treatment, centrifugation and air-drying of the thread reveals strong red-orange fluorescence under UV light.
Example 3:
The impregnation of a patchwork fabric containing several distinct bands of synthetic, artificial, natural (vegetal and animal) fibers (20g) is performed at 25°C for 10-60 min in the same liquour and liquour ratio to textile material as described in Example 1. After treatment, centrifugation and air-drying of the patchwork reveals on most fibers strong red-orange fluorescence under UV light.
Equivalent results are obtained from similar processes using other lanthanide complexes, exhibiting other emission wavelength under irradiation in the UV (e.g. terbium, dysprosium, samarium, neodymium).
Example 4:
High temperature dyeing (HTD) of a polyester (PES) filament (135°C, 60min)
A PES filament (10g) is introduced in a 250mL bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex of formula XVII dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogencarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
Example 5:
High temperature dyeing (HTD) of a velvet PES fabric (135°C, 60min)
A velvet PES fabric (10g) is introduced in a 250ml bottle tight against leakage, containing
200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30mL) containing 3-5% of the lanthanide complex of formula XVII dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
Example 6:
High temperature dyeing (HTD) of a velvet PES fabric (135"C, 60min)
A white velvet PES fabric (10g) is introduced in a 250mL bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogencarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated velvet PES fabric is white and exhibits a strong green fluorescence under irradiation at 254nm.
Example 7:
High temperature dyeing (HTD) of a polyamide (PA) tricot (135°C, 60min)
A PA tricot (10g) is introduced in a 250mL bottle tight against leakage, containing 200mL of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XVII dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogencarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated PA tricot exhibits a strong red-orange fluorescence under irradiation at 365nm.
Example 8:
High temperature dyeing (HTD) of a PA tricot (135"C, 60min)
A white PA tricot (10g) is introduced in a 250ml bottle tight against leakage, containing
200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30mL) containing 3-5% of the lanthanide complex XV dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated PA tricot is white and exhibits a green fluorescence under irradiation at 254nm.
Example 9:
High temperature dyeing (HTD) of a transparent colourless PA thread (135°C, 60min)
A transparent colourless PA thread (10g) is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XVII dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated transparent PES thread exhibits a strong red-orange fluorescence under irradiation at 365nm.
Example 10:
Incorporation of XVII in polyamide (PA) by mass-dyeing process
Extruded Ultramid B3K in the presence of 2% of the lanthanide complex XII for 2 min at
260°C results in red-orange fluorescence upon irradiation at 365nm.
Example 11 :
Incorporation of XVII in polystyrene (PS) by mass-dyeing process
Extruded Polystyrol H165 in the presence of 2% of the lanthanide complex XVII for 5 min at 300°C results in red-orange fluorescence upon irradiation at 365nm.
Example 12:
Incorporation of XVII in polypropylene (PP) by mass-dyeing process
A homogenised mixture of polypropylene granules (200g) and compound XVII (2g) is introduced in the fusion chamber (200°C) of a 3mm cable extruder. After cooling in a water bath, the thus obtained rigid cable is cut into granules again, which are in turn introduced in the fusion chamber (230°C) of a filament extruder. The thus obtained transparent multifilament thin polypropylene thread (δdtex) exhibits a strong red-orange fluorescence upon excitation at 365nm.
Example 13:
Incorporation of XVII in polypropylene (PP) by mass-dyeing process
Similar process and resulting fluorescent properties are obtained with simultaneous use of
Titanium dioxide together with compound XVII.
Example 14:
Incorporation of XVII in poly(methylmethacrylate) (PMMA) by mass-dyeing process Extruded Plexiglas 6N in the presence of 2% of the lanthanide complex XVII for 5 min at 260°C results in red-orange fluorescence upon irradiation at 365nm.
Example 15:
Incorporation of XVII in acrylonitrile/butadiene/styrene-copolymer (ABS) by mass-dyeing process
Extruded Terluran 877M in the presence of 2% of the lanthanide complex XVII for 5 min at
220°C results in red-orange fluorescence upon irradiation at 365nm.
Example 16:
High temperature dyeing (HTD) of a coloured PES thin thread (135"C, 60min)
A thin cyan PES thread (10g) - previously mass-dyed with a mixture of Irgalite Blue GLGP
(C.I. Pigment Blue 15:3), titanium dioxide (C.I. Pigment White 6) and carbon black (C.I.
Pigment Black 7) - is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions: o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogencarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated thin cyan PES thread is cyan and exhibits a strong green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
Example 17:
High temperature dyeing (HTD) of a coloured PES thin thread (135°C, 60min)
A thin black PES thread (10g) - previously mass-dyed with a pigment mixture containing titanium dioxide (C.I. Pigment White 6) and carbon black (C.I. Pigment Black 7) - is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions: o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated thin black PES thread is
black and exhibits a strong green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
Example 18:
High temperature dyeing (HTD) of a coloured PES thin thread (135°C, 60min)
A thin yellow PES thread (10g) - previously mass-dyed with Filester Yellow RNB(C./.
Pigment Yellow 147) - is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions: o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170ml) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogencarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated thin yellow PES thread is yellow and exhibits a strong green-yellow fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
Example 19:
High temperature dyeing (HTD) of a PES filament (135°C, 60min)
A PES filament (10g) is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex
dissolved in NMP o an aqueous solution at pH=4.5 (195 to 170mL) containing
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
Example 20:
High temperature dyeing (HTD) of a PES filament (135°C, 60min)
A white PES filament (10g) is introduced in a 250m! bottle tight against leakage, containing
200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a NMP suspension (5 to 30ml) containing 2% of the lanthanide complex
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C),
spin dried and finally dried with hot air (90-105°C). The thus treated white PES filament is white and exhibits a pink-red fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
Example 21 :
High temperature dyeing (HTD) of a PES filament (135°C, 60min)
A white PES filament (1 Og) is introduced in a 250ml bottle tight against leakage, containing
200ml of dyeing bath (i.e. bath ratio 1 to 20).
The dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex
(H5C2)2NH Tb3+
■ 0.6g/l of Univadin DP (Ciba Specialty Chemicals)
■ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals)
■ 0.4g/l sodium hydrogenocarbonate
The bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C. The temperature is then raised to 135°C over 30 min and kept stable for further 1 hour. The treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C). The thus treated white PES filament is white and exhibits a green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
Example 22:
High temperature dyeing (HTD) of PES (135°C, 60min)
All above experiments of High Temperature Dyeing are also realised without using NMP, by a similar preparation method to that of Disperse Dyes, and by replacing the Disperse Dye with the UV fluorescent lanthanide chelate to be applied.
Example 23:
Transfer printing with UV fluorescent lanthanide chelates is performed by using transfer printing formulations containing one or more UV fluorescent lanthanide chelates. These formulations are prepared in a similar way to conventional transfer printing formulations, either by using one or more lanthanide chelates in place of disperse dyes, or by using one or more lanthanide chelates in addition to the disperse dye(s).
Example 24:
Preparation of a multi-component security thread
A polymer mixture (e.g. copolymerised polyamide Akulon®, supplied by Akzoplastiks) is distributed to three extruders and the granules are melted. The melts indicated for the outer components of the thread are each mixed with 3 % by weight of a compound of formula
(XVII) in such a way that it dissolves homogeneously in the polyamide melt. After extrusion of the multi-component threads a security thread is obtained the edge strips of which fluoresce under UV light whereas the central strip does not show any fluorescence.
Co-extrusion of the lanthanide chelate(s) with one or more dyes or pigments provides coloured threads which are similarly fluorescent under UV light.
Example 25:
Preparation of a multi-component security thread
As described in Example 24, a security thread is prepared by extrusion of a polyamide melt containing 3 % by weight of a 1:1 mixture of a compound of formula (XVII) and a compound of formula (XV). Upon irradiation of UV light of different wavelengths red and/or green fluorescence is observed.
Claims
1. A process for the preparation of luminescent polymeric fibres characterised in that the fibres are treated with a composition comprising
(a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one UV absorbing group and
(b) one or more solvents.
2. A process according to claim 1 characterized in that component (a) is a compound of formula I
Lm-Ln3+(Ch-)n (I), wherein Ln represents a lanthanide,
Ch" is a negatively charged ligand containing at least one UV absorbing double bond, n denotes 3 or 4, m denotes a number from 0 to 4, in case n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4, m denotes 1 and L is a single-charged cation.
3. A process according to claim 1 characterized in that component (a) is a compound of formula II, III or IV
wherein Ln represents a lanthanide, n denotes 3 or 4, m denotes a number from 0 to 4
in case n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4, m denotes 1 and
L is a single-charged cation,
R , is hydrogen or C,-C6alkyl, and
Ri and R3 are each independently of the other hydrogen, C C6alkyl, CF3, C5-C2 aryl or
C4-C2 heteroaryl.
4. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, III or IV wherein n denotes 3 and L is a nitrogen-containing ligand.
5. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, III or IV wherein L is a compound of formulae V to XII
6. A process according to claim 5 characterized in that component (a) is a compound of formula II wherein L is a compound of formula V, VI, VII, VIM, IX, X, XI or XII wherein R , R5 and R6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N+(R7)3.wherein R7 is d-C6alkyl.
7. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm or Nd.
8. A process according to claim 3 characterized in that component (a) is a compound of formula II or III wherein R, and R3 are methyl, t-butyl, n-pentyl or phenyl.
9. A process according to claim 3 characterized in that component (a) is a compound of formula II wherein R2 is hydrogen.
10. A process according to claim 3 characterized in that component (a) is a compound of formula XIII to Lll
CH, (XXIV),
(XXVlll),
Tb* (XXXI), Tb (XXXll),
Tb (XXXIll), (XXXIV),
Eu3+ I ( HH,3C
3+ (XXXVlll),
Eu ( (H3C
Eu (XXXX),
(XXXXII),
Dy +
(XXXXIV),
Dy3+
D (XXXXV), Dy3+ (XXXXVI),
(XXXXVIll),
Nd3+ / ( HH,3C'
11. A process according to claim 1 or 2 characterized in that component (b) is water, one or more water-miscible organic solvents or a mixture of water and one or more water-miscible organic solvents.
12. A process according to claim 11 characterized in that the water-miscible organic solvent is an aliphatic alcohol, etheralcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatic sulfoxide.
13. A process according to claim 11 characterized in that the water-miscible organic solvent is selected from the group consisting of ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofurane (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile, polyethyleneglycol dimethyether and dimethylsulfoxide (DMSO).
14. A process according to claim 1 characterized in that the formulation contains 0.01 to 20.0 % by weight of component (a) and 80.0 to 99.99 % by weight of component (b), based on the total amount of components (a) + (b).
15. A process according to claim 1 characterized in that the formulation contains additionally (c) one or more colorants.
16. A process for the preparation of luminescent plastics characterized in that the plastics material is extruded in the presence of 0.01 - 10.0 % by weight, based on the amount of polymeric material, of a compound of formula II or III according to claim 3.
17. A luminescent textile fibre prepared by the process according to claim 1.
8. A luminescent plastic prepared by the process according to claim 16.
19. A process according to claim 1 wherein the polymeric fibres are paper fibres or synthetic fibres.
20. The use of the process according to claim 1 for the preparation of anti-counterfeit documents, cards, cheques or banknotes.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0315835-7A BRPI0315835A2 (en) | 2003-06-20 | 2003-10-21 | process for incorporating UV luminescent compounds into polymeric materials |
| MXPA05004229A MXPA05004229A (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials. |
| EP03795792A EP1560894A2 (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials |
| CA002502038A CA2502038A1 (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials |
| AU2003298093A AU2003298093A1 (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials |
| US10/531,905 US20060046050A1 (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials |
| JP2005501809A JP4381377B2 (en) | 2002-10-30 | 2003-10-21 | Method of incorporating UV luminescent compound into polymer material |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02405931 | 2002-10-30 | ||
| EP02405931.3 | 2002-10-30 | ||
| EP03405448 | 2003-06-20 | ||
| EP03405448.6 | 2003-06-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004039913A2 true WO2004039913A2 (en) | 2004-05-13 |
| WO2004039913A3 WO2004039913A3 (en) | 2004-07-01 |
Family
ID=32232211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/011638 WO2004039913A2 (en) | 2002-10-30 | 2003-10-21 | Process for incorporation of uv-luminescent compounds in polymeric materials |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20060046050A1 (en) |
| EP (1) | EP1560894A2 (en) |
| JP (1) | JP4381377B2 (en) |
| KR (1) | KR101076621B1 (en) |
| AR (1) | AR041843A1 (en) |
| AU (1) | AU2003298093A1 (en) |
| CA (1) | CA2502038A1 (en) |
| MX (1) | MXPA05004229A (en) |
| TW (1) | TW200418952A (en) |
| WO (1) | WO2004039913A2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034865A1 (en) * | 2006-09-21 | 2008-03-27 | Institut National Des Sciences Appliquees De Rennes | Method for labelling a material comprising at least one non-organic matrix and corresponding material |
| EP2116578A1 (en) * | 2008-05-09 | 2009-11-11 | CMS Technology Inc. | Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same |
| US7981208B2 (en) | 2007-04-30 | 2011-07-19 | Nanocms Co., Ltd. | Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same |
| WO2015200579A3 (en) * | 2014-06-27 | 2016-03-10 | Eastman Chemical Company | Fibers with chemical markers used for coding |
| EP3152357A1 (en) * | 2014-06-04 | 2017-04-12 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Method for marking a textile thread with a fluorescent element, textile thread produced by the marking method, and use of said textile thread for weaving an item of clothing |
| US9633579B2 (en) | 2014-06-27 | 2017-04-25 | Eastman Chemical Company | Fibers with physical features used for coding |
| CN107083237A (en) * | 2017-05-06 | 2017-08-22 | 中北大学 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
| US9863920B2 (en) | 2014-06-27 | 2018-01-09 | Eastman Chemical Company | Fibers with chemical markers and physical features used for coding |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE502005005905D1 (en) * | 2005-10-26 | 2008-12-18 | Alcan Tech & Man Ltd | Object with a printed image |
| ITMI20080572A1 (en) * | 2008-04-02 | 2009-10-03 | Colograf S R L | DECORATED WOODEN CONTAINER. |
| US20120070378A1 (en) * | 2008-12-16 | 2012-03-22 | The University Of Akron | Lanthanide ion complexes and imaging method |
| CN107022096B (en) * | 2017-06-01 | 2020-03-27 | 厦门大学 | Preparation of high-light-permeability composite cellulose acetate membrane with near-ultraviolet excitation function |
| EP3584088B1 (en) * | 2018-06-19 | 2020-09-30 | Borealis AG | Polyolefin composition providing marking by fluorescence |
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| EP0066854A1 (en) * | 1981-06-05 | 1982-12-15 | GAO Gesellschaft für Automation und Organisation mbH | Security paper and method for its manufacture |
| US4655788A (en) * | 1984-06-22 | 1987-04-07 | Michel Jalon | Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications |
| US4833311A (en) * | 1986-08-19 | 1989-05-23 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
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| JPH0212197B2 (en) * | 1980-05-30 | 1990-03-19 | Gee Aa Oo G Fuyuuru Automatsuioon Unto Oruganizatsuioon Mbh | |
| DE3446861A1 (en) * | 1984-12-21 | 1986-07-10 | GAO Gesellschaft für Automation und Organisation mbH, 8000 München | SECURITY DOCUMENT WITH THE SECURITY THREAD STORED IN IT AND METHOD FOR THE PRODUCTION AND AUTHENTICITY TESTING OF THE SECURITY DOCUMENT |
| BE1007071A3 (en) * | 1993-04-28 | 1995-03-07 | Philips Electronics Nv | Optical systems. |
| DE69600437T2 (en) * | 1995-01-06 | 1998-12-10 | Ciba Geigy Ag | TRIBOLUMINESCENT LANTHANID III COMPLEXES |
| US5837042A (en) * | 1996-06-10 | 1998-11-17 | Videojet Systems International, Inc. | Invisible fluorescent jet ink |
| US5759349A (en) * | 1995-12-14 | 1998-06-02 | Westvaco Corporation | Lumen loading of hygienic end use paper fibers |
| US6045656A (en) * | 1998-12-21 | 2000-04-04 | Westvaco Corporation | Process for making and detecting anti-counterfeit paper |
| US6402986B1 (en) * | 1999-07-16 | 2002-06-11 | The Trustees Of Boston University | Compositions and methods for luminescence lifetime comparison |
| CA2473180A1 (en) * | 2002-02-26 | 2003-09-04 | Ciba Specialty Chemicals Holding Inc. | Ink compositions containing lanthanide complexes |
-
2003
- 2003-10-21 MX MXPA05004229A patent/MXPA05004229A/en unknown
- 2003-10-21 EP EP03795792A patent/EP1560894A2/en not_active Withdrawn
- 2003-10-21 AU AU2003298093A patent/AU2003298093A1/en not_active Abandoned
- 2003-10-21 CA CA002502038A patent/CA2502038A1/en not_active Abandoned
- 2003-10-21 WO PCT/EP2003/011638 patent/WO2004039913A2/en active Application Filing
- 2003-10-21 JP JP2005501809A patent/JP4381377B2/en not_active Expired - Fee Related
- 2003-10-21 KR KR1020057007609A patent/KR101076621B1/en not_active IP Right Cessation
- 2003-10-21 US US10/531,905 patent/US20060046050A1/en not_active Abandoned
- 2003-10-28 TW TW092129837A patent/TW200418952A/en unknown
- 2003-10-28 AR ARP030103931A patent/AR041843A1/en unknown
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|---|---|---|---|---|
| EP0066854A1 (en) * | 1981-06-05 | 1982-12-15 | GAO Gesellschaft für Automation und Organisation mbH | Security paper and method for its manufacture |
| US4655788A (en) * | 1984-06-22 | 1987-04-07 | Michel Jalon | Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications |
| US4833311A (en) * | 1986-08-19 | 1989-05-23 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
| US4891505A (en) * | 1986-08-19 | 1990-01-02 | Petrel | Security markings, material provided with security marks, and apparatus to detect the security mark |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034865A1 (en) * | 2006-09-21 | 2008-03-27 | Institut National Des Sciences Appliquees De Rennes | Method for labelling a material comprising at least one non-organic matrix and corresponding material |
| FR2906393A1 (en) * | 2006-09-21 | 2008-03-28 | Inst Nat Sciences Appliq | METHOD OF MARKING A MATERIAL COMPRISING AT LEAST ONE MINERAL MATRIX AND MATERIAL THEREFOR |
| US8211702B2 (en) | 2006-09-21 | 2012-07-03 | Institut National Des Sciences Appliquees De Rennes | Method for labelling a material comprising at least one non-organic matrix and corresponding material |
| US7981208B2 (en) | 2007-04-30 | 2011-07-19 | Nanocms Co., Ltd. | Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same |
| EP2116578A1 (en) * | 2008-05-09 | 2009-11-11 | CMS Technology Inc. | Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same |
| EP3152357A1 (en) * | 2014-06-04 | 2017-04-12 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Method for marking a textile thread with a fluorescent element, textile thread produced by the marking method, and use of said textile thread for weaving an item of clothing |
| WO2015200579A3 (en) * | 2014-06-27 | 2016-03-10 | Eastman Chemical Company | Fibers with chemical markers used for coding |
| US9633579B2 (en) | 2014-06-27 | 2017-04-25 | Eastman Chemical Company | Fibers with physical features used for coding |
| US9851341B2 (en) | 2014-06-27 | 2017-12-26 | Eastman Chemical Company | Fibers with chemical markers used for coding |
| US9863920B2 (en) | 2014-06-27 | 2018-01-09 | Eastman Chemical Company | Fibers with chemical markers and physical features used for coding |
| US9916482B2 (en) | 2014-06-27 | 2018-03-13 | Eastman Chemical Company | Fibers with physical features used for coding |
| US10127410B2 (en) | 2014-06-27 | 2018-11-13 | Eastman Chemical Company | Fibers with physical features used for coding |
| US10527593B2 (en) | 2014-06-27 | 2020-01-07 | Eastman Chemical Company | Method of making fibers with chemical markers and physical features used for coding |
| US11231408B2 (en) | 2014-06-27 | 2022-01-25 | Eastman Chemical Company | Fibers with chemical markers used for coding |
| CN107083237A (en) * | 2017-05-06 | 2017-08-22 | 中北大学 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004039913A3 (en) | 2004-07-01 |
| EP1560894A2 (en) | 2005-08-10 |
| MXPA05004229A (en) | 2005-07-05 |
| TW200418952A (en) | 2004-10-01 |
| CA2502038A1 (en) | 2004-05-13 |
| US20060046050A1 (en) | 2006-03-02 |
| AU2003298093A8 (en) | 2004-05-25 |
| JP2006504883A (en) | 2006-02-09 |
| KR20050084907A (en) | 2005-08-29 |
| KR101076621B1 (en) | 2011-10-26 |
| AR041843A1 (en) | 2005-06-01 |
| AU2003298093A1 (en) | 2004-05-25 |
| JP4381377B2 (en) | 2009-12-09 |
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