EP2217757A1 - Method for metallising a polymer - Google Patents
Method for metallising a polymerInfo
- Publication number
- EP2217757A1 EP2217757A1 EP08853073A EP08853073A EP2217757A1 EP 2217757 A1 EP2217757 A1 EP 2217757A1 EP 08853073 A EP08853073 A EP 08853073A EP 08853073 A EP08853073 A EP 08853073A EP 2217757 A1 EP2217757 A1 EP 2217757A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- polymer
- amine
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 125000003277 amino group Chemical group 0.000 claims abstract description 43
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000007259 addition reaction Methods 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 150000002815 nickel Chemical class 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 20
- -1 silver halide Chemical class 0.000 claims description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- SYQIWVMFOAHDMK-UHFFFAOYSA-N 2,2,3,3-tetramethyloxirane Chemical compound CC1(C)OC1(C)C SYQIWVMFOAHDMK-UHFFFAOYSA-N 0.000 claims description 2
- UWMHHZFHBCYGCV-UHFFFAOYSA-N 2,3,2-tetramine Chemical compound NCCNCCCNCCN UWMHHZFHBCYGCV-UHFFFAOYSA-N 0.000 claims description 2
- ZBHSAYWIYAVUOP-UHFFFAOYSA-N 2-(benzylamino)-1-[3-(trifluoromethyl)phenyl]ethanol Chemical compound C=1C=CC(C(F)(F)F)=CC=1C(O)CNCC1=CC=CC=C1 ZBHSAYWIYAVUOP-UHFFFAOYSA-N 0.000 claims description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 2
- NMLOXRWLGGSMAK-UHFFFAOYSA-N 3-trimethylsilyl-n-(3-trimethylsilylpropyl)propan-1-amine Chemical compound C[Si](C)(C)CCCNCCC[Si](C)(C)C NMLOXRWLGGSMAK-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical compound O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 claims description 2
- 229930007453 limonene-1,2-epoxide Natural products 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- NQXGLOVMOABDLI-UHFFFAOYSA-N sodium oxido(oxo)phosphanium Chemical compound [Na+].[O-][PH+]=O NQXGLOVMOABDLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002759 woven fabric Substances 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 239000005068 cooling lubricant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001465 metallisation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 125000006850 spacer group Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229920006659 PA12 Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000009975 flexible effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011140 metalized polyester Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/385—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing epoxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
- D10B2501/021—Hosiery; Panti-hose
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
- D10B2501/043—Footwear
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/08—Upholstery, mattresses
Definitions
- the present invention relates to a process for metallizing a polymer. Furthermore, the present invention relates to a polymer prepared by a process for metallization and its use. Furthermore, the present invention relates to a polymer which is coated with a metal.
- US 4,681,591 describes a process for producing a metallized polyester fiber textile comprising the steps of: pretreating the textile material comprising at least 15% by weight of polyester fibers and any other fiber type which may be selected from cotton, polyamide 6, Polyamide 66, acrylic fibers and glass fibers, with an aqueous solution of caustic alkali, activating treatment of the pretreated fabric with a stannous-containing compound and with a palladium-containing compound and non-electrolytically coating the activating treated fabric in a mixture comprising nickel, copper , Cobalt, chromium or their alloys to form a metal coating thereon.
- a textile material produced in this way is suitable as protection against electromagnetic radiation.
- DE 34 19 755 A1 discloses a method for silvering non-metallic materials.
- a surface to be silvered is activated with at least one compound based on palladium and then silvered using a silver plating bath.
- the silver plating bath contains, in addition to a silver salt, thiocyanate ions as complexing agent and hydroxylamine as reducing agent.
- WO 2006/052548 A1 discloses a process for modifying polymer surfaces for the deposition of metal, in which a polymer is modified with an etchant, the modified polymer is silylated to provide a polymer having amino groups, and a noble metal is deposited on the amino group-containing polymer.
- DE 600 02 681 T2 describes a method for producing a carrier material with biocidal properties, in which chitosan is deposited on the carrier material, the carrier material is immersed in a silver salt solution, the silver salt is reduced, the chitosan is cross-linked, and the carrier material is washed.
- DE 689 14 485 T2 describes a process for the metallization of fibrous material in which the fibrous material is coated with polymers which may be functionalized. Subsequently, a metallization is performed.
- DE 38 14 506 A1 describes a method for metallizing substrate surfaces, in which the surfaces are treated with a primer based on a polymeric organic film former prior to activation with complex compounds.
- the metal loading or the degree of metallization of polymers depends in particular on the adhesiveness of the metal or the metal compound to the polymer or an optional intermediate layer. Insufficient adhesiveness may result in increased and uncontrolled metal or metal ion release when the metallized material is used, for example, in a liquid. In particular, with regard to environmental and disposal aspects, but also on the cost-effectiveness of such materials, an uncontrolled release of metal or metal ions is disadvantageous.
- the uncontrolled, often too high, delivery of metal or metal ions into a liquid prevents the use of metallized polymer in liquid-containing systems because such polymers do not meet the system specifications or guidelines and regulations which, for example, have been adopted by the EU to protect the environment or the consumer, such as EU Directive 98/83 on drinking water.
- the polymer in the process for metallizing a polymer, is treated in succession, at least by the following means: with at least one compound having at least one amine group,
- Treatment of the polymer with a compound having at least one amine group and with a compound having at least one functional group capable of performing an addition reaction with the amine group provides the polymer with a functionalized layer.
- metal is fixed via interactions, in particular via coordinative or ionic interactions, with the functional groups of the functionalized layer.
- the ionic metal is reduced to form a metal layer.
- a metal-coated polymer having a low metal releasing ability can be used - A - be obtained. That is, the metal adheres excellently to the obtained polymer.
- Articles of the present invention are also the metallized polymer obtained by the process and its use.
- the metallized polymer is used for the antimicrobial treatment of liquid in fluid-carrying systems or for the production of stockings, insoles, clothing, upholstery for seating or mattresses.
- the above uses are advantageous on the one hand by the excellent adhesion of the silver to the polymer obtained according to the invention and a reduced release of silver to the environment and on the other hand by the biocidal action of the silver.
- the polymer is treated before treatment with a compound having at least one amine group with at least one compound having at least one functional group which is suitable to perform an addition reaction with the amine group. That is, the order of these two treatment steps is interchangeable.
- the polymer may be treated first with the compound having at least one amine group and then with at least one compound having at least one functional group capable of performing an addition reaction with the amine group, or vice versa.
- the treatment of the polymer first with the compound having at least one functional group capable of performing an addition reaction with the amine group and then with a compound having at least one amine group is particularly advantageously carried out when the compound having at least an amine group has strong basic properties and the polymer is not resistant to bases.
- the respective treatment is preferably carried out at room temperature.
- the treatment time can be 1 minute to 10 hours.
- the compound having at least one amine group is, in an advantageous embodiment, a liquid, polyfunctional amine.
- a liquid, polyfunctional amine can be applied neat to the optionally treated polymer, which leads to a high degree of loading, excludes possible side reactions of a solvent and avoids waste products such as a solvent used and working steps such as removal of a solvent.
- the degree of the polyfunctionality by selecting the degree of the polyfunctionality, the hydrophobicity / hydrophilicity and the degree of crosslinking of the addition product with the compound having at least one functional group capable of performing an addition reaction with the amine group can be adjusted.
- the adjustment of the degree of crosslinking plays a role, in particular with regard to the brittleness of the added product produced.
- the liquid polyfunctional amine is a compound having two primary amine functions and at least one secondary amine function linked together by straight chain carbon chains having 2 or 3 carbon atoms are.
- the at least one compound having at least one amine group is a compound of the formula R 1 NHR 2 (I),
- R 1 is selected from the group consisting of H 2 N (CH 2 ) W, R 3 3Si (CH 2 ) w and H 2 NC 6 H 4 ,
- R 2 is selected from the group consisting of [(CH 2 ) x NH] y (CH 2 ) z NH 2 ,
- R 1 is H 2 N (CH 2 ) W
- R 2 is [(CH 2 ) x NH] y (CH 2 ) z NH 2 , where w, x, y and z are as defined above
- R 1 R 3 3 is Si (CH 2 ) w
- R 2 R 3 is 3 Si (CH 2 ) y , wherein R 3 , w and y are as defined above, ie the compound of formula (I) has silane or silanol functions.
- the compound of formula (I) is selected from the group consisting of bis (3-aminopropyl) amine, N, N'-bis (2-aminoethyl) -1, 3-propanediamine, triethylenetetramine, tetraethylenepentamine, bis [3- (trimethoxysilyl) propyl] amine and bis [3- (trimethylsilyl) propyl] amine.
- Particularly advantageous is the compound of formula (I) bis (3-aminopropyl) amine or tetraethylenepentamine.
- an addition reaction of the compound which has at least one amine group is carried out by contacting with a compound which has at least one isocyanate group. That is, in this embodiment, a compound having at least one functional group is is suitable to carry out an addition reaction with the amine group, a compound having at least one isocyanate group.
- a compound having at least one amine group makes an addition reaction with a compound having at least one isocyanate group to form a urea.
- the compound having at least one isocyanate group a diisocyanate.
- the diisocyanate is selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate).
- the diisocyanate is hexamethylene diisocyanate. Hexamethylene diisocyanate forms, in particular with the polyfunctional amines described above, a layer on the polymer which is firmly adherent but flexible, and not brittle. Brittle layers tend to crumble easily from polymeric support structures.
- the polymer is coated with the compound having at least one amine group, optionally padded, and with a compound having at least one isocyanate group has, coated and optionally padded, the coating sequence is exchangeable. Thereafter, the thus treated polymer is washed, preferably with water. Optionally, the polymer is then dried. Whether a padding or merely a coating of the polymer with the respective compound is carried out depends on the carrier structure of the polymer. For example, when the polymer is in the form of a yarn, it is advantageous to perform a padding because a padding is the result Increased adhesion of the respective compound to the possibly already treated polymer.
- the coating of the polymer with the respective compound is understood to mean the spraying, wetting, setting or dipping of the polymer into the respective compound.
- the coating of the polymer with the respective compound can take place over the whole area or part of the area.
- the coating of the treated polymer with a compound having at least one amine group or with a compound having at least one isocyanate group is carried out by dipping, laying, spraying or wetting the polymer with the corresponding compound.
- the corresponding compound may be dissolved in a solvent.
- the solvent used is preferably water.
- the concentration of each compound ranges from 100% to 0.1%.
- an addition reaction of the compound having at least one amine group is carried out by contacting with a compound having at least one epoxy group.
- a compound having an epoxide group examples include propylene oxide, styrene oxide, 4-vinyl-1-cyclohexene-1, 2-epoxide, 2,3-dimethyl-2,3-epoxybutane and limonene-1, 2-epoxide.
- Further examples of a compound having at least one epoxide group are epoxy resins, in particular monomolecular or lower-polymeric diglycidyl compounds having terminal epoxy groups.
- an epoxy resin are bisphenol glycidyl ether type epoxy resins, as are preferably available from epichlorohydrin and bisphenol A. Such epoxy resins are commercially available.
- the polymer is either sprayed, wetted, dipped or laid with the compound having at least one amine group, already treated or subsequently treated with the compound having at least one epoxy group.
- the compound having at least one epoxy group may be dissolved in a solvent.
- the solvent is an aprotic
- Solvent more preferably an organic solvent.
- a usable solvent include aliphatic solvents having 1 to 10 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cycloheptane, cyclooctane, dichloromethane, chloroform, 1, 2-dichloroethane, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran or dioxane and aromatic solvents such as benzene, toluene, xylene or the like, which of course may also be used in combination.
- the metal salt is selected from the group consisting of silver halide, silver sulfate, silver nitrate, copper halide, copper sulfate, copper nitrate, copper acetate, nickel halide, nickel sulfate, nickel nitrate and nickel acetate.
- the metal salt used is particularly advantageously silver nitrate, silver chloride or silver sulfate. More preferably, the metal salt is silver nitrate.
- Halide used according to the invention comprises, in particular, chloride, bromide or iodide.
- the complexing agent used in the process according to the invention is in an advantageous embodiment selected from the group consisting of ammonia, ethylenediamine, triethanolamine, ethanolamine, 1, 3-diaminopropane, sodium thiosulfate, thioisocyanate, glycerol, sodium tartrate, sodium potassium tartrate and sodium citrate.
- the complexing agent ammonia is volatile. Therefore, excess ammonia can be easily removed.
- the solution containing the metal salt and the complexing agent is advantageously an aqueous solution.
- Particularly advantageous comprises the above solution Water, the metal salt and the complexing agent.
- the ratio of metal salt to complexing agent is advantageously in the range of 1: 1 to 1:10, more preferably 1: 2 to 1: 3 (v / v).
- the treatment of the polymer with the metal salt and complexing agent-containing solution is advantageously carried out at a temperature between 10 0 C and 60 0 C, more preferably between 20 ° C and 50 0 C.
- the treatment time is between 5 minutes and 5 hours, advantageously between 15 minutes and 3 hours.
- the treatment is advantageously carried out by dipping or immersing the treated polymer in the solution.
- the polymer is dried after treatment with the metal salt and complexing agent-containing solution. The drying is advantageous in a
- the drying time is advantageously between 10 minutes and 30 minutes.
- Treatment of the functional group-endowed polymer with the solution containing the metal salt and the complexing agent fixes the metal through interactions, particularly through coordinative and ionic interactions, respectively.
- the reducing agent is selected from the group consisting of glucose, ascorbic acid, sodium borohydride, sodium dithionite, sodium sulfite, sodium formate, formaldehyde and sodium hydrophosphite.
- the reducing agent serves to reduce the ionic metal.
- the reducing agent is glucose or ascorbic acid.
- Glucose or ascorbic acid is a very environmentally friendly reducing agent, easy to handle, readily available and non-toxic.
- the reduction is preferably carried out in water, in particular at temperatures between 10 ° C and 60 0 C, preferably 20 ° C and 30 ° C, over a period between 5 minutes and 1 day, preferably between 30 Minutes and 1 hour.
- the reducing agent is preferably in the form of an aqueous solution with a concentration of 1, 25 to 5 g / l and a pH in the range of 7 to 12, preferably, 8 to 10.5, used.
- the pH of the reducing agent-containing solution can be adjusted, for example, by means of the addition of ammonia.
- the reducing agent is sodium borohydride
- the reduction is preferably carried out in ethanol, in particular at temperatures between 10 0 C and 50 0 C, preferably 20 ° C and 30 0 C, over a period of time between 5 minutes and 2
- the polymer is advantageously dipped or inserted into the reducing agent-containing solution and optionally agitated.
- the treatment of the polymer is carried out at a liquor ratio (ratio of the mass (kg) of the product to the volume (I) of the reducing agent solution) of 1:10 to 1: 100, preferably 1:50 to 1: 100.
- the resulting metallized polymer is washed in an advantageous embodiment with water and optionally heated to drying up to 150 ° C.
- the process according to the invention is advantageously subjected to a polymer which is selected from the group consisting of polyamide, polyester, polacryl, polyurethane, polyolefin, polyether and mixtures thereof.
- the polymer optionally further contains one or more conventional auxiliaries, processing or additives.
- the polymer is particularly advantageously a polyamide, polyester or polyolefin.
- For the purposes of the present invention comprise polyamide, polyester or polyolefin both homopolymers and copolymers.
- the polyamide PA 6, PA11, PA12, PA66, PA46, PA6 / 6T, PA6 / 6I, PA1212, PA612, PA6I, PA6I / 6T, PA 6, PA11, PA12, PA66 or PA46 is preferably used.
- the polyester is preferably polyethylene terephthalate,
- the polyolefin used is preferably polypropylene or polyethylene, more preferably polypropylene. In particular polyacrylonitrile is used as the acrylic.
- the usual auxiliary, processing or additives include stabilizers, flame retardants, processing aids, antistatic agents, antioxidants, plasticizers, Dyes, impact modifiers, adhesion modifiers, pigments, reinforcing agents and / or fillers include, but are not limited to.
- Preferred examples of the usual auxiliaries, processing or additives include short glass fibers, glass beads, carbon fibers, carbon black, chalk, mica, talc, barite, mica, wollastonite, calcium carbonate, titanium dioxide,
- additive also includes thread materials of all kinds, which can be integrated into the polymer textile technology.
- the polymer is treated with an agent selected from the group consisting of reducing agent, complexing agent and polymer.
- agent selected from the group consisting of reducing agent, complexing agent and polymer.
- the active principles of the agent are the reduction of any remaining ionic metal portions in the region of the surface of the metallized polymer, the removal of any remaining ionic metal portions of the metallized polymer by means of complexing or a sealing of the metallized polymer.
- such a treatment of the metallized polymer serves as a method for the reduction of metal ions, for the complexation of metal ions or for sealing a metal coating to effect a purpose-oriented, depending on the application field controlled metal delivery.
- a depot effect in the application means that a metal delivery permitted in accordance with the respective guidelines, system specifications and regulations is constant over a long period of time. As a result, a long duration of action and thus a long useful life of the metallized polymer is achieved.
- Particularly advantageous is the treatment of the metallized polymer with a reducing agent.
- reducing agents mentioned above are used as the reducing agent.
- the treatment conditions are the same as mentioned above.
- a preferred reducing agent is glucose.
- the reducing action of aqueous solutions of glucose depends, inter alia, on the glucose concentration and the pH-dependent redox potential, which depends linearly on the pH.
- the silver release of the polymerized polymer after treatment with the reducing agent decreases linearly with increasing pH of the reducing solution and with increasing oxidation potential. That is, by treating the metallized polymer with the reducing agent, the metal or metal ion release, in this case the silver ion or silver ion release, of the metallized polymer into a surrounding liquid can be adjusted to a certain value.
- the agent is a complexing agent.
- the complexing agent used is a chelating agent mentioned above.
- the metallized polymer is rinsed with the complexing agent, which may be in aqueous solution. Subsequently, the treated polymer is optionally washed with water and optionally dried at a temperature of up to 140 0 C.
- the agent is a polymer.
- the polymer is preferably selected from the group consisting of polyurethane, polyacrylate and finishing equipment.
- a metallized polymer is obtained.
- a besilfertes, bekupfertes or benickeltes polymer is obtained by the method according to the invention.
- Particularly preferred is a besilbertes by the method according to the invention
- the metallized polymer may be a full-area or partially metallized polymer.
- the metallized polymer obtained by the process according to the invention is advantageously in the form of a yarn, a fiber, a filament, a woven fabric, a knitted fabric, a braid, a knitted fabric or a fleece.
- the metallized polymer obtained by the process according to the invention is a fiber. It is then particularly suitable for the production of stockings and clothing.
- the resulting metallized polymer is a knitted fabric, in particular a knitted spacer fabric. The spacer fabric is particularly useful for antimicrobial treatment of fluid in fluid-carrying systems and insoles.
- the present invention also relates to a coated polymer comprising a polymer comprising a layer of an addition product of a compound having at least one amine group and a compound having at least one functional group which is suitable with the amine group an addition reaction and having a layer of at least one metal selected from the group consisting of silver, copper and nickel.
- a coated polymer comprising a polymer comprising a layer of an addition product of a compound having at least one amine group and a compound having at least one functional group which is suitable with the amine group an addition reaction and having a layer of at least one metal selected from the group consisting of silver, copper and nickel.
- the coated polymer comprises a polymer having a layer of urea and a layer of silver.
- the urea is preferably obtained by an addition reaction of at least one compound having at least one amine group with at least one compound having at least one isocyanate group.
- the urea is an addition product of at least one compound of the formula
- R 1 is selected from the group consisting of H 2 N (CH 2 ) W , R 3 3 Si (CH 2 ) w and H 2 NC 6 H 4
- R 2 is selected from the group consisting of [(CH 2) ⁇ NH] y (CH 2 ) z NH 2 , R 3 3 Si (CH 2 ) y and H 2 NC 6 H 4 NH (CH 2 ) Y
- w is an integer from 1 to 7, preferably 2 or 3
- x is an integer from 1 to 7, preferably 2 or 3
- y is zero or an integer from 1 to 7, preferably zero, 1 or 2
- z is one is integer from 1 to 7, preferably 2 or 3
- R 3 is a branched or straight-chain alkyl or -O-alkyl of 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms, and a compound selected from the group consisting of
- a polymer obtained using the method of the invention is suitable for the antimicrobial treatment of liquids in one
- the metallized polymer is used to make stockings, insoles, clothing, upholstery for seating or mattresses.
- a besilbertes polymer is particularly suitable because of the particularly strong oligodynamic properties.
- the metallized polymer is used in particular in the treatment of a liquid in the form of a useful liquid or in the form of drinking water.
- These fluids may be present in closed or open, stagnant, or recirculating systems in power plants, industrial, commercial, or air conditioning systems.
- the metal elution of the polymer according to the invention can be adjusted individually such that, for example, when used for the treatment of liquid in the form of drinking water, different national regulations regarding the maximum permissible metal concentration in drinking water are adhered to.
- useful liquid serves as a generic term for a liquid which fulfills one or more functionalities such as, for example, cooling, lubricating, hydraulically switching and controlling, or which is consumed as a process or process fluid.
- the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid cooling lubricant in the cooling lubricant circuit of a metal-working plant.
- a liquid cooling lubricant in the cooling lubricant circuit of a metal-working plant.
- Such lubricating fluids are commonly used in industrial and commercial plants that process metals by a substance engagement, such as by turning, milling or drilling.
- Particularly advantageous is the use when the cooling lubricant liquid is used as a water-oil emulsion in a cooling lubricant system.
- the cooling lubricant remains characterized, without the usual biocides, especially on formaldehyde-based, are necessary microbiologically stable. This results in lower health burdens on operating personnel and lower costs due to longer service life.
- the delivery of antimicrobial metal components can be optimally adjusted according to the requirements.
- a further preferred use is that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid switching medium in the hydraulic circuit of an industrial plant. Also in hydraulic circuits it happens that biomass growth is a problem. This applies in particular to circuits with areas through which material is routinely introduced into the hydraulic medium which is suitable for feeding large quantities of microorganisms. This applies, for example, to systems containing cellulose
- a further preferred use provides that the antimicrobial treatment of a liquid in a liquid-conducting system in a laundry washing plant comprises the treatment of retained wash rinse water.
- This makes it possible to store the retained Waschgut- rinse water in a reservoir, without running the risk that this water due to microbial activity in the long term unusable. This is especially true when, for example, when rinsing the laundry substances are washed out, which represent a good food base for microorganisms. This is the case in particular when washing natural fiber textiles.
- the treated wash rinse water will be used as wash water for a new beginning wash cycle of the car wash.
- the rinse water of the last rinse cycle for use as the first wash water is stored in a new wash, a further reduction of water consumption of washing machines can be realized in a simple manner. This effect can be transferred to other washing systems and washing processes for different laundry items.
- a further preferred use provides that the antimicrobial treatment of a liquid in a fluid-carrying system in a medical device comprises the treatment of germ-free working water. It is regularly necessary to ensure high requirements with regard to a permanent sterility of the water and a thus coming in contact with the pipeline system. This can be ensured in a simple and reliable manner by the use of a three-dimensional suture system with oligodynamic activity.
- the present invention will now be explained in more detail with reference to an embodiment. However, the present invention is not limited to the embodiment.
- a polyester spacer fabric was immersed in hexamethylene diisocyanate (20% in water) for 1 minute and then in bis (3-aminopropyl) amine for 3 hours.
- the thus-treated polyester was allowed to dry at 20 ° C. for 1 day.
- the thus treated polyester was heated in a mixture of aqueous silver nitrate solution (5%) and ammonia solution (25%) at a liquor ratio of 1: 1 for 3 hours at 50 0 C with stirring.
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Abstract
The invention relates to a method for metallising a polymer, in which the polymer is sequentially treated with the following: at least one compound that has at least one amine group; a compound that has at least one functional group, suitable for carrying out an addition reaction with the amine group; a solution containing at least one metal salt, selected from the group consisting of a silver salt, a copper salt and a nickel salt, and a complexing agent; at least one reductant. The invention also relates to polymers that have been metallised according to the invention and to their use for the anti-microbial treatment of liquids in liquid-conducting systems or for the production of hosiery, insoles, clothing and covers for seating or mattresses.
Description
Verfahren zur Metallisierung eines Polymers Process for metallizing a polymer
Die vorliegende Erfindung betrifft ein Verfahren zur Metallisierung eines Polymers. Weiterhin betrifft die vorliegende Erfindung ein nach einem Verfahren zur Metallisierung hergestelltes Polymer sowie dessen Verwendung. Weiterhin betrifft die vorliegende Erfindung ein Polymer, das mit einem Metall beschichtet ist.The present invention relates to a process for metallizing a polymer. Furthermore, the present invention relates to a polymer prepared by a process for metallization and its use. Furthermore, the present invention relates to a polymer which is coated with a metal.
Im Stand der Technik sind Verfahren zur Metallisierung von Polymeren sowie metallisierte Polymere bekannt.In the prior art, methods for the metallization of polymers and metallized polymers are known.
So beschreibt die US 4,681 ,591 ein Verfahren zur Herstellung eines metallisierten Polyesterfaser-Textilmaterials, das folgende Schritte aufweist: Vorbehandlung des Textilmaterials, das wenigstens 15 Gew.-% Polyesterfasern und irgendeinen anderen Fasertyp umfasst, der ausgewählt sein kann aus Baumwolle, Polyamid 6, Polyamid 66, Acrylfasern und Glasfasern, mit einer wässrigen Lösung aus Ätzalkali, Aktivierungsbehandlung des vorbehandelten Textilmaterials mit einer Zinn(ll)-haltigen Verbindung und mit einer Palladium- haltigen Verbindung und nicht-elektrolytisches Überziehen des aktivierungsbehandelten Textilmaterials in einer Mischung, die Nickel, Kupfer, Cobalt, Chrom oder deren Legierungen enthält, um eine Metallbeschichtung darauf zu bilden. Ein derart hergestelltes Textilmaterial eignet sich als Schutz gegen elektromagnetische Strahlen.Thus, US 4,681,591 describes a process for producing a metallized polyester fiber textile comprising the steps of: pretreating the textile material comprising at least 15% by weight of polyester fibers and any other fiber type which may be selected from cotton, polyamide 6, Polyamide 66, acrylic fibers and glass fibers, with an aqueous solution of caustic alkali, activating treatment of the pretreated fabric with a stannous-containing compound and with a palladium-containing compound and non-electrolytically coating the activating treated fabric in a mixture comprising nickel, copper , Cobalt, chromium or their alloys to form a metal coating thereon. A textile material produced in this way is suitable as protection against electromagnetic radiation.
Die DE 34 19 755 A1 offenbart ein Verfahren zur Versilberung von nichtmetallischen Werkstoffen. Dabei wird eine zu versilbernde Oberfläche mit mindestens einer Verbindung auf Basis von Palladium aktiviert und anschließend unter Verwendung eines Versilberungsbades versilbert. Das Versilberungsbad enthält neben einem Silbersalz Thiocyanationen als Komplexbildner und Hydroxylamin als Reduktionsmittel.DE 34 19 755 A1 discloses a method for silvering non-metallic materials. In this case, a surface to be silvered is activated with at least one compound based on palladium and then silvered using a silver plating bath. The silver plating bath contains, in addition to a silver salt, thiocyanate ions as complexing agent and hydroxylamine as reducing agent.
In der WO 2006/052548 A1 wird ein Verfahren zur Modifizierung von Polymeroberflächen zur Abscheidung von Metall offenbart, bei dem ein Polymer
mit einem Ätzmittel modifiziert wird, das modifizierte Polymer zur Bereitstellung eines Polymers mit Aminogruppen silyliert wird, und ein Edelmetall auf dem Aminogruppen enthaltenden Polymer abgeschieden wird.WO 2006/052548 A1 discloses a process for modifying polymer surfaces for the deposition of metal, in which a polymer is modified with an etchant, the modified polymer is silylated to provide a polymer having amino groups, and a noble metal is deposited on the amino group-containing polymer.
DE 600 02 681 T2 beschreibt ein Verfahren zur Herstellung eines Trägermaterials mit Biozideigenschaften, bei dem Chitosan auf dem Trägermaterial abgeschieden wird, das Trägermaterial in eine Silbersalzlösung eingetaucht wird, das Silbersalz reduziert wird, das Chitosan quervernetzt wird, und das Trägermaterial gewaschen wird.DE 600 02 681 T2 describes a method for producing a carrier material with biocidal properties, in which chitosan is deposited on the carrier material, the carrier material is immersed in a silver salt solution, the silver salt is reduced, the chitosan is cross-linked, and the carrier material is washed.
In der DE 689 14 485 T2 wird ein Verfahren zur Metallisierung von faserartigem Material beschrieben, bei dem das faserartige Material mit Polymeren beschichtet wird, welche funktionalisiert sein können. Anschließend wird eine Metallisierung durchgeführt.DE 689 14 485 T2 describes a process for the metallization of fibrous material in which the fibrous material is coated with polymers which may be functionalized. Subsequently, a metallization is performed.
Die DE 38 14 506 A1 beschreibt ein Verfahren zum Metallisieren von Substratoberflächen, bei dem vor der Aktivierung mit Komplexverbindungen die Oberflächen mit einem Primer auf der Basis eines polymeren organischen Filmbildners behandelt werden.DE 38 14 506 A1 describes a method for metallizing substrate surfaces, in which the surfaces are treated with a primer based on a polymeric organic film former prior to activation with complex compounds.
Die Metallbeladung bzw. der Metallisierungsgrad von Polymeren hängt insbesondere von der Haftfähigkeit des Metalls bzw. der Metallverbindung an dem Polymer oder einer optionalen Zwischenschicht ab. Eine ungenügende Haftfähigkeit kann zu einer erhöhten und unkontrollierten Metall- bzw. Metallionenabgabe bei Einsatz des metallisierten Materials beispielsweise in einer Flüssigkeit führen. Insbesondere im Hinblick auf Umwelt- und Entsorgungsaspekte, aber auch auf die Wirtschaftlichkeit derartiger Materialien, ist eine unkontrollierte Abgabe von Metall bzw. Metallionen nachteilig.The metal loading or the degree of metallization of polymers depends in particular on the adhesiveness of the metal or the metal compound to the polymer or an optional intermediate layer. Insufficient adhesiveness may result in increased and uncontrolled metal or metal ion release when the metallized material is used, for example, in a liquid. In particular, with regard to environmental and disposal aspects, but also on the cost-effectiveness of such materials, an uncontrolled release of metal or metal ions is disadvantageous.
Insbesondere verhindert die unkontrollierte, oftmals auch zu hohe Abgabe von Metall bzw. Metallionen in eine Flüssigkeit den Einsatz von metallisiertem Polymer in Flüssigkeit führenden Systemen, weil derartige Polymere nicht die Systemvorgaben oder Richtlinien und Verordnungen erfüllen, die, zum Beispiel,
zum Schutz der Umwelt oder des Verbrauchers von der EU erlassen worden sind, wie beispielsweise die EU-Richtlinie 98/83 für Trinkwasser.In particular, the uncontrolled, often too high, delivery of metal or metal ions into a liquid prevents the use of metallized polymer in liquid-containing systems because such polymers do not meet the system specifications or guidelines and regulations which, for example, have been adopted by the EU to protect the environment or the consumer, such as EU Directive 98/83 on drinking water.
Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, ein verbessertes Verfahren zur Metallisierung eines Polymers, insbesondere ein Verfahren zur Metallisierung eines Polymers zur Verfügung zu stellen, mit dem ein homogener Metallüberzug auf dem Polymer und eine hohe Haftfähigkeit zwischen Metall und Polymer erreicht werden kann.It is therefore an object of the present invention to provide an improved process for metallizing a polymer, in particular a process for metallizing a polymer, with which a homogeneous metal coating on the polymer and a high adhesion between metal and polymer can be achieved.
Diese Aufgabe wird durch ein Verfahren mit den Merkmalen von Anspruch 1 gelöst.This object is achieved by a method having the features of claim 1.
Erfindungsgemäß wird bei dem Verfahren zur Metallisierung eines Polymers das Polymer mindestens mit den nachfolgenden Mitteln nacheinander behandelt: • mit mindestens einer Verbindung, die mindestens eine Amingruppe aufweist,According to the invention, in the process for metallizing a polymer, the polymer is treated in succession, at least by the following means: with at least one compound having at least one amine group,
• mit einer Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen,With a compound which has at least one functional group which is suitable for carrying out an addition reaction with the amine group,
• mit einer Lösung, die mindestens ein Metallsalz, das ausgewählt ist aus der Gruppe bestehend aus einem Silbersalz, einem Kupfersalz und einem Nickelsalz, und einen Komplexbildner enthält, undWith a solution containing at least one metal salt selected from the group consisting of a silver salt, a copper salt and a nickel salt, and a complexing agent, and
• mit mindestens einem Reduktionsmittel.• with at least one reducing agent.
Die Behandlung des Polymers mit einer Verbindung, die mindestens eine Amingruppe aufweist, und mit einer Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, rüstet das Polymer mit einer funktionalisierten Schicht aus. Durch Behandlung mit einer Lösung, die ein Metallsalz und einen Komplexbildner enthält, wird Metall über Wechselwirkungen, insbesondere über koordinative bzw. ionische Wechselwirkungen, mit den funktionellen Gruppen der funktionalisierten Schicht fixiert. Anschließend wird das ionische Metall zur Bildung einer Metallschicht reduziert. Durch das erfindungsgemäße Verfahren kann ein mit Metall überzogenes Polymer mit einem geringen Metallfreigabevermögen
- A - erhalten werden. D. h., das Metall haftet hervorragend an dem erhaltenen Polymer.Treatment of the polymer with a compound having at least one amine group and with a compound having at least one functional group capable of performing an addition reaction with the amine group provides the polymer with a functionalized layer. By treatment with a solution containing a metal salt and a complexing agent, metal is fixed via interactions, in particular via coordinative or ionic interactions, with the functional groups of the functionalized layer. Subsequently, the ionic metal is reduced to form a metal layer. By the method of the present invention, a metal-coated polymer having a low metal releasing ability can be used - A - be obtained. That is, the metal adheres excellently to the obtained polymer.
Gegenstände der vorliegenden Erfindung sind ebenfalls das durch das Verfahren erhaltene metallisierte Polymer und dessen Verwendung. Das metallisierte Polymer wird zur antimikrobiellen Behandlung von Flüssigkeit in Flüssigkeitführenden Systemen oder zur Herstellung von Strümpfen, Einlegesohlen, Kleidung, Bezugstextilien für Sitzmöbel oder Matratzen verwendet. Insbesondere bei dem erfindungsgemäß erhaltenen besilberten Polymer sind die vorstehenden Verwendungen einerseits durch die erzielte hervorragende Haftung des Silbers an dem erfindungsgemäß erhaltenen Polymer und eine dadurch erzielbare verminderte Abgabe von Silber an die Umgebung und andererseits durch die biozide Wirkung des Silbers vorteilhaft.Articles of the present invention are also the metallized polymer obtained by the process and its use. The metallized polymer is used for the antimicrobial treatment of liquid in fluid-carrying systems or for the production of stockings, insoles, clothing, upholstery for seating or mattresses. Particularly in the case of the silvered polymer obtained according to the present invention, the above uses are advantageous on the one hand by the excellent adhesion of the silver to the polymer obtained according to the invention and a reduced release of silver to the environment and on the other hand by the biocidal action of the silver.
Weitere vorteilhafte Ausgestaltungen der vorliegenden Erfindung sind in den Unteransprüchen angegeben.Further advantageous embodiments of the present invention are specified in the subclaims.
In einer vorteilhaften Ausführungsform wird das Polymer vor der Behandlung mit einer Verbindung, die mindestens eine Amingruppe aufweist, mit mindestens einer Verbindung behandelt, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen. Das heißt, die Reihenfolge dieser beiden Behandlungsschritte ist austauschbar. Das Polymer kann zuerst mit der Verbindung, die mindestens eine Amingruppe aufweist, und anschließend mit mindestens einer Verbindung behandelt werden, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, oder umgekehrt. Die Behandlung des Polymers zuerst mit der Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, und anschließend mit einer Verbindung, die mindestens eine Amingruppe aufweist, wird insbesondere vorteilhaft ausgeführt, wenn die Verbindung mit der mindestens einen Amingruppe stark basische Eigenschaften aufweist und das Polymer nicht beständig gegenüber Basen ist. Bevorzugt wird die Behandlung des Polymeren mit einer Verbindung, die
mindestens eine Amingruppe aufweist, und die Behandlung des Polymeren mit mindestens einer Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, durch Besprühen, Benetzen, Legen oder Tauchen des Polymeren in die jeweilige Verbindung, die ggf. in einem Lösungsmittel gelöst ist, durchgeführt. Die jeweilige Behandlung wird vorzugsweise bei Raumtemperatur durchgeführt. Die Behandlungszeit kann 1 Minute bis 10 Stunden betragen.In an advantageous embodiment, the polymer is treated before treatment with a compound having at least one amine group with at least one compound having at least one functional group which is suitable to perform an addition reaction with the amine group. That is, the order of these two treatment steps is interchangeable. The polymer may be treated first with the compound having at least one amine group and then with at least one compound having at least one functional group capable of performing an addition reaction with the amine group, or vice versa. The treatment of the polymer first with the compound having at least one functional group capable of performing an addition reaction with the amine group and then with a compound having at least one amine group is particularly advantageously carried out when the compound having at least an amine group has strong basic properties and the polymer is not resistant to bases. Preference is given to treating the polymer with a compound which has at least one amine group, and the treatment of the polymer with at least one compound having at least one functional group which is suitable to perform an addition reaction with the amine group, by spraying, wetting, laying or immersing the polymer in the respective compound, if necessary . is dissolved in a solvent carried out. The respective treatment is preferably carried out at room temperature. The treatment time can be 1 minute to 10 hours.
Die Verbindung, die mindestens eine Amingruppe aufweist, ist in einer vorteilhaften Ausführungsform ein flüssiges, polyfunktionelles Amin. Ein flüssiges, polyfunktionelles Amin kann einerseits pur auf das ggf. behandelte Polymer aufgebracht werden, was zu einem hohen Beladungsgrad führt, mögliche Nebenreaktionen eines Lösungsmittels ausschließt sowie Abfallprodukte wie ein verwendetes Lösungsmittel und Arbeitsschritte wie Entfernung eines Lösungsmittels vermeidet. Andererseits kann mittels der Wahl des Grads der Polyfunktionalität die Hydrophobizität/Hydrophilizität und der Vernetzungsgrad des Additionsprodukts mit der Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, eingestellt werden. Die Einstellung des Vernetzungsgrads spielt insbesondere im Hinblick auf die Sprödigkeit des erzeugten Additionsprodukts eine Rolle. Je höher der Vernetzungsgrad der Verbindung, die mindestens eine Amingruppe aufweist, mit der Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, ist, desto spröder wird das erzeugte Additionsprodukt. Um ein Additionsprodukt mit einer ausreichend flexiblen Eigenschaft zu erreichen, handelt es sich in einer vorteilhaften Ausführungsform bei dem flüssigen, polyfunktionellen Amin um eine Verbindung, die zwei primäre Aminfunktionen und mindestens eine sekundäre Aminfunktion aufweist, welche über geradkettige Kohlenstoffketten mit 2 oder 3 Kohlenstoffatomen miteinander verbunden sind.The compound having at least one amine group is, in an advantageous embodiment, a liquid, polyfunctional amine. On the one hand, a liquid, polyfunctional amine can be applied neat to the optionally treated polymer, which leads to a high degree of loading, excludes possible side reactions of a solvent and avoids waste products such as a solvent used and working steps such as removal of a solvent. On the other hand, by selecting the degree of the polyfunctionality, the hydrophobicity / hydrophilicity and the degree of crosslinking of the addition product with the compound having at least one functional group capable of performing an addition reaction with the amine group can be adjusted. The adjustment of the degree of crosslinking plays a role, in particular with regard to the brittleness of the added product produced. The higher the degree of crosslinking of the compound having at least one amine group with the compound having at least one functional group capable of performing an addition reaction with the amine group, the more brittle the generated addition product becomes. In an advantageous embodiment, to achieve an addition product having a sufficiently flexible property, the liquid polyfunctional amine is a compound having two primary amine functions and at least one secondary amine function linked together by straight chain carbon chains having 2 or 3 carbon atoms are.
Vorteilhafter ist die mindestens eine Verbindung, die mindestens eine Amingruppe aufweist, eine Verbindung der Formel
R1NHR2 (I),More preferably, the at least one compound having at least one amine group is a compound of the formula R 1 NHR 2 (I),
wobei R1 ausgewählt ist aus der Gruppe, bestehend aus H2N(CH2)W, R33Si(CH2)w und H2NC6H4,wherein R 1 is selected from the group consisting of H 2 N (CH 2 ) W, R 3 3Si (CH 2 ) w and H 2 NC 6 H 4 ,
R2 ausgewählt ist aus der Gruppe, bestehend aus [(CH2)xNH]y(CH2)zNH2,R 2 is selected from the group consisting of [(CH 2 ) x NH] y (CH 2 ) z NH 2 ,
R3 3Si(CH2)z und H2NC6H4NH(CH2)Z, w eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, x eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, y Null oder eine ganze Zahl von 1 bis 7 ist, bevorzugt Null, 1 oder 2 ist, z eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, R3 ein verzweigtes oder geradkettiges Alkyl oder -O-Alkyl mit 1 bis 10 Kohlenstoffatomen, bevorzugt mit 1 bis 8 Kohlenstoffatomen, bevorzugter mit 1 oder 2 Kohlenstoffatomen, ist.R 3 3 Si (CH 2 ) z and H 2 NC 6 H 4 NH (CH 2 ) Z , w is an integer from 1 to 7, preferably 2 or 3, x is an integer from 1 to 7, preferably 2 or 3, is, y is zero or an integer from 1 to 7, preferably zero, 1 or 2, z is an integer from 1 to 7, preferably 2 or 3, R 3 is a branched or straight-chain alkyl or O-alkyl of 1 to 10 carbon atoms, preferably of 1 to 8 carbon atoms, more preferably of 1 or 2 carbon atoms.
Wenn R1 H2N(CH2)W ist, dann ist in einer vorteilhaften Ausführungsform R2 [(CH2)xNH]y(CH2)zNH2, wobei w, x, y und z wie vorstehend definiert sind. Wenn R1 R3 3Si(CH2)w ist, dann ist in einer anderen vorteilhaften Ausführungsform R2 R3 3Si(CH2)y, wobei R3, w und y wie vorstehend definiert sind, d.h. die Verbindung der Formel (I) weist Silan- bzw. Silanolfunktionen auf.When R 1 is H 2 N (CH 2 ) W , then in an advantageous embodiment R 2 is [(CH 2 ) x NH] y (CH 2 ) z NH 2 , where w, x, y and z are as defined above , When R 1 R 3 3 is Si (CH 2 ) w , then in another advantageous embodiment R 2 R 3 is 3 Si (CH 2 ) y , wherein R 3 , w and y are as defined above, ie the compound of formula (I) has silane or silanol functions.
Vorteilhaft ist die Verbindung der Formel (I) ausgewählt aus der Gruppe, bestehend aus Bis(3-aminopropyl)amin, N,N'-Bis(2-aminoethyl)-1 ,3- propandiamin, Triethylentetramin, Tetraethylenpentamin, Bis[3- (trimethoxysilyl)propyl]amin und Bis[3-(trimethylsilyl)propyl]amin. Besonders vorteilhaft ist die Verbindung der Formel (I) Bis(3-aminopropyl)amin oder Tetraethylenpentamin.Advantageously, the compound of formula (I) is selected from the group consisting of bis (3-aminopropyl) amine, N, N'-bis (2-aminoethyl) -1, 3-propanediamine, triethylenetetramine, tetraethylenepentamine, bis [3- (trimethoxysilyl) propyl] amine and bis [3- (trimethylsilyl) propyl] amine. Particularly advantageous is the compound of formula (I) bis (3-aminopropyl) amine or tetraethylenepentamine.
In einer vorteilhaften Ausgestaltung des erfindungsgemäßen Verfahrens wird eine Additionsreaktion der Verbindung, die mindestens eine Amingruppe aufweist, durch Kontaktierung mit einer Verbindung, die mindestens eine Isocyanatgruppe aufweist, durchgeführt. D.h., in dieser Ausführungsform ist eine Verbindung, die mindestens eine funktionelle Gruppe aufweist, die
geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, eine Verbindung, die mindestens eine Isocyanatgruppe aufweist. Eine Verbindung, die mindestens eine Amingruppe aufweist, führt mit einer Verbindung mit mindestens einer Isocyanatgruppe eine Additionsreaktion unter Bildung eines Harnstoffs aus. Wenn die Verbindung, die mindestens eine Amingruppe aufweist, mindestens zwei Amingruppen aufweist, und die Verbindung, die mindestens eine Isocyanatgruppe aufweist, mindestens zwei Isocyanatgruppen aufweist, kann ein Harnstoffnetzwerk gebildet werden. Die Ausbildung eines Netzwerks hat den Vorteil, dass eine Schichtstruktur gebildet wird, die eine gleichmäßige BeSchichtung des Polymers darstellt.In an advantageous embodiment of the process according to the invention, an addition reaction of the compound which has at least one amine group is carried out by contacting with a compound which has at least one isocyanate group. That is, in this embodiment, a compound having at least one functional group is is suitable to carry out an addition reaction with the amine group, a compound having at least one isocyanate group. A compound having at least one amine group makes an addition reaction with a compound having at least one isocyanate group to form a urea. When the compound having at least one amine group has at least two amine groups and the compound having at least one isocyanate group has at least two isocyanate groups, a urea network can be formed. The formation of a network has the advantage that a layer structure is formed which represents a uniform coating of the polymer.
Vorteilhaft ist die Verbindung, die mindestens eine Isocyanatgruppe aufweist, ein Diisocyanat. Bevorzugt ist das Diisocyanat ausgewählt aus der Gruppe, bestehend aus Hexamethylendiisocyanat, Tolylendiisocyanat, Isophorondiisocyanat und 4,4'-Methylenbis(cyclohexylisocyanat). Besonders bevorzugt ist das Diisocyanat Hexamethylendiisocyanat. Hexamethylendiidsocyanat bildet insbesondere mit den vorstehend beschriebenen polyfunktionellen Aminen eine Schicht auf dem Polymer, die fest haftet, aber flexibel, und nicht spröde, ist. Spröde Schichten neigen dazu, leicht von polymeren Trägerstrukturen abzubröckeln.Advantageously, the compound having at least one isocyanate group, a diisocyanate. Preferably, the diisocyanate is selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate). Most preferably, the diisocyanate is hexamethylene diisocyanate. Hexamethylene diisocyanate forms, in particular with the polyfunctional amines described above, a layer on the polymer which is firmly adherent but flexible, and not brittle. Brittle layers tend to crumble easily from polymeric support structures.
Zur Durchführung einer Additionsreaktion der Verbindung, die mindestens eine Amingruppe aufweist, mit einer Verbindung, die mindestens eine Isocyanatgruppe aufweist, wird das Polymer mit der Verbindung, die mindestens eine Amingruppe aufweist, beschichtet, gegebenenfalls foulardiert, und mit einer Verbindung, die mindestens eine Isocyanatgruppe aufweist, beschichtet und gegebenenfalls foulardiert, wobei die Beschichtungsreihenfolge austauschbar ist. Danach wird das so behandelte Polymer, vorzugsweise mit Wasser, gewaschen. Optional wird das Polymer dann getrocknet. Ob eine Foulardierung oder lediglich eine Beschichtung des Polymeren mit der jeweiligen Verbindung durchgeführt wird, hängt von der Trägerstruktur des Polymers ab. Wenn beispielsweise das Polymer in Form eines Garns vorliegt, wird vorteilhaft eine Foulardierung durchgeführt, weil eine Foulardierung die
Haftung der jeweiligen Verbindung an dem ggf. bereits behandelten Polymer erhöht. Wenn das Polymer in Form eines Abstandgewirkes vorliegt, wird keine Foulardierung durchgeführt, weil sie zu einer Zerstörung der Trägerstruktur führen würde. In dem erfindungsgemäßen Verfahren ist es folglich nicht notwendig eine Foulardierung bei der Behandlung des Polymeren mit der jeweiligen Verbindung durchzuführen, kann aber zu besseren Hafteigenschaften zwischen der jeweiligen Verbindung und dem Polymeren führen. Im Sinne der vorliegenden Erfindung wird unter Beschichtung des Polymeren mit der jeweiligen Verbindung das Besprühen, Benetzen, Legen oder Tauchen des Polymeren in die jeweilige Verbindung verstanden. Die Beschichtung des Polymeren mit der jeweiligen Verbindung kann ganzflächig oder teilflächig erfolgen.To carry out an addition reaction of the compound having at least one amine group with a compound having at least one isocyanate group, the polymer is coated with the compound having at least one amine group, optionally padded, and with a compound having at least one isocyanate group has, coated and optionally padded, the coating sequence is exchangeable. Thereafter, the thus treated polymer is washed, preferably with water. Optionally, the polymer is then dried. Whether a padding or merely a coating of the polymer with the respective compound is carried out depends on the carrier structure of the polymer. For example, when the polymer is in the form of a yarn, it is advantageous to perform a padding because a padding is the result Increased adhesion of the respective compound to the possibly already treated polymer. If the polymer is in the form of a spacer knit, no padding is performed because it would lead to destruction of the support structure. In the process of the present invention, therefore, it is not necessary to perform padding in the treatment of the polymer with the respective compound, but may lead to better adhesive properties between the respective compound and the polymer. For the purposes of the present invention, the coating of the polymer with the respective compound is understood to mean the spraying, wetting, setting or dipping of the polymer into the respective compound. The coating of the polymer with the respective compound can take place over the whole area or part of the area.
Die Beschichtung des behandelten Polymers mit einer Verbindung, die mindestens eine Amingruppe aufweist, bzw. mit einer Verbindung, die mindestens eine Isocyanatgruppe aufweist, wird durch Tauchen, Legen, Besprühen oder Benetzen des Polymers mit der entsprechenden Verbindung durchgeführt. Optional kann die entsprechende Verbindung in einem Lösungsmittel gelöst sein. Als Lösungsmittel wird vorzugsweise Wasser eingesetzt. Die Konzentration der jeweiligen Verbindung reicht von 100 % bis 0,1%.The coating of the treated polymer with a compound having at least one amine group or with a compound having at least one isocyanate group is carried out by dipping, laying, spraying or wetting the polymer with the corresponding compound. Optionally, the corresponding compound may be dissolved in a solvent. The solvent used is preferably water. The concentration of each compound ranges from 100% to 0.1%.
Alternativ wird eine Additionsreaktion der Verbindung, die mindestens eine Amingruppe aufweist, durch Kontaktierung mit einer Verbindung durchgeführt, die mindestens eine Epoxidgruppe aufweist. Beispiele für eine Verbindung, die eine Epoxidgruppe aufweist, sind Propylenoxid, Styroloxid, 4-Vinyl-1 - cyclohexen-1 ,2-epoxid, 2,3-Dimethyl-2,3-epoxybutan und Limonen-1 ,2-epoxid. Weitere Beispiele für eine Verbindung, die mindestens eine Epoxidgruppe aufweist, sind Epoxidharze, insbesondere monomolekulare oder niederpolymere Diglycidyl-Verbindungen mit endständigen Epoxy-Gruppen. Bevorzugte Beispiele für ein Epoxidharz stellen Epoxidharze vom Bisphenolglycidether-Typ dar, wie sie bevorzugt aus Epichlorhydrin und Bisphenol A erhältlich sind. Derartige Epoxidharze sind kommerziell erhältlich. Bevorzugt wird das Polymer, das
entweder mit einer Verbindung, die mindestens eine Amingruppe aufweist, bereits behandelt wurde oder anschließend behandelt wird, mit der Verbindung, die mindestens eine Epoxidgruppe aufweist, besprüht, benetzt, getaucht oder gelegt. Die Verbindung, die mindestens eine Epoxidgruppe aufweist, kann dabei in einem Lösungsmittel gelöst sein. Als Lösungsmittel wird ein aprotischesAlternatively, an addition reaction of the compound having at least one amine group is carried out by contacting with a compound having at least one epoxy group. Examples of a compound having an epoxide group are propylene oxide, styrene oxide, 4-vinyl-1-cyclohexene-1, 2-epoxide, 2,3-dimethyl-2,3-epoxybutane and limonene-1, 2-epoxide. Further examples of a compound having at least one epoxide group are epoxy resins, in particular monomolecular or lower-polymeric diglycidyl compounds having terminal epoxy groups. Preferred examples of an epoxy resin are bisphenol glycidyl ether type epoxy resins, as are preferably available from epichlorohydrin and bisphenol A. Such epoxy resins are commercially available. Preferably, the polymer is either sprayed, wetted, dipped or laid with the compound having at least one amine group, already treated or subsequently treated with the compound having at least one epoxy group. The compound having at least one epoxy group may be dissolved in a solvent. The solvent is an aprotic
Lösungsmittel, bevorzugter ein organisches Lösungsmittel gewählt. Beispiele für ein verwendbares Lösungsmittel schließen aliphatische Lösungsmittel mit 1 bis 10 Kohlenstoffatomen, wie beispielsweise Pentan, Hexan, Heptan, Octan, Nonan, Decan, Cyclopentan, Cycloheptan, Cyclooctan, Dichlormethan, Chloroform, 1 ,2-Dichlorethan, Diethylether, Methyl-tert-butylether, Tetrahydrofuran oder Dioxan sowie aromatische Lösungsmittel, wie beispielsweise Benzol, Toluol, Xylol oder dergleichen, ein, welche selbstverständlich auch in Kombination verwendet werden können.Solvent, more preferably an organic solvent. Examples of a usable solvent include aliphatic solvents having 1 to 10 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cycloheptane, cyclooctane, dichloromethane, chloroform, 1, 2-dichloroethane, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran or dioxane and aromatic solvents such as benzene, toluene, xylene or the like, which of course may also be used in combination.
Bei einer vorteilhaften Ausführungsform der vorliegenden Erfindung ist das Metallsalz ausgewählt aus der Gruppe, bestehend aus Silberhalogenid, Silbersulfat, Silbernitrat, Kupferhalogenid, Kupfersulfat, Kupfernitrat, Kupferacetat, Nickelhalogenid, Nickelsulfat, Nickelnitrat und Nickelacetat. Besonders vorteilhaft ist das verwendete Metallsalz Silbernitrat, Silberchlorid oder Silbersulfat. Noch bevorzugter ist das Metallsalz Silbernitrat.In an advantageous embodiment of the present invention, the metal salt is selected from the group consisting of silver halide, silver sulfate, silver nitrate, copper halide, copper sulfate, copper nitrate, copper acetate, nickel halide, nickel sulfate, nickel nitrate and nickel acetate. The metal salt used is particularly advantageously silver nitrate, silver chloride or silver sulfate. More preferably, the metal salt is silver nitrate.
Erfindungsgemäß eingesetztes Halogenid umfasst insbesondere Chlorid, Bromid oder lodid.Halide used according to the invention comprises, in particular, chloride, bromide or iodide.
Der bei dem erfindungsgemäßen Verfahren eingesetzte Komplexbildner ist in einer vorteilhaften Ausführungsform ausgewählt aus der Gruppe, bestehend aus Ammoniak, Ethylendiamin, Triethanolamin, Ethanolamin, 1 ,3-Diaminopropan, Natriumthiosulfat, Thioisocyanat, Glycerol, Natriumtartrat, Natriumkaliumtartrat und Natriumeitrat. Besonders vorteilhaft ist der Komplexbildner Ammoniak. Ammoniak ist leicht flüchtig. Daher kann überschüssiges Ammoniak leicht entfernt werden.The complexing agent used in the process according to the invention is in an advantageous embodiment selected from the group consisting of ammonia, ethylenediamine, triethanolamine, ethanolamine, 1, 3-diaminopropane, sodium thiosulfate, thioisocyanate, glycerol, sodium tartrate, sodium potassium tartrate and sodium citrate. Particularly advantageous is the complexing agent ammonia. Ammonia is volatile. Therefore, excess ammonia can be easily removed.
Die Lösung, die das Metallsalz und den Komplexbildner enthält, ist vorteilhaft eine wässrige Lösung. Besonders vorteilhaft umfasst die vorstehende Lösung
Wasser, das Metallsalz und den Komplexbildner. Das Verhältnis von Metallsalz zu Komplexbildner liegt vorteilhaft in dem Bereich von 1 :1 bis 1 :10, vorteilhafter 1 :2 bis 1 :3 (v/v). Die Behandlung des Polymers mit der Metallsalz- und Komplexbildner-haltigen Lösung wird vorteilhaft bei einer Temperatur zwischen 100C und 600C, vorteilhafter zwischen 20° C und 500C, durchgeführt. Die Behandlungszeit liegt zwischen 5 Minuten und 5 Stunden, vorteilhaft zwischen 15 Minuten und 3 Stunden. Die Behandlung wird vorteilhaft durch Eintauchen bzw. Einlegen des behandelten Polymers in die Lösung durchgeführt. Optional wird das Polymer nach der Behandlung mit der Metallsalz- und Komplexbildner- haltigen Lösung getrocknet. Die Trocknung wird vorteilhaft bei einerThe solution containing the metal salt and the complexing agent is advantageously an aqueous solution. Particularly advantageous comprises the above solution Water, the metal salt and the complexing agent. The ratio of metal salt to complexing agent is advantageously in the range of 1: 1 to 1:10, more preferably 1: 2 to 1: 3 (v / v). The treatment of the polymer with the metal salt and complexing agent-containing solution is advantageously carried out at a temperature between 10 0 C and 60 0 C, more preferably between 20 ° C and 50 0 C. The treatment time is between 5 minutes and 5 hours, advantageously between 15 minutes and 3 hours. The treatment is advantageously carried out by dipping or immersing the treated polymer in the solution. Optionally, the polymer is dried after treatment with the metal salt and complexing agent-containing solution. The drying is advantageous in a
Temperatur zwischen 30°C und 60°C, vorteilhafter zwischen 400C und 55°C durchgeführt. Die Trocknungszeit liegt vorteilhaft zwischen 10 Minuten und 30 Minuten.Temperature between 30 ° C and 60 ° C, more advantageously carried out between 40 0 C and 55 ° C. The drying time is advantageously between 10 minutes and 30 minutes.
Durch die Behandlung des mit funktionellen Gruppen ausgerüsteten Polymers mit der Lösung, die das Metallsalz und den Komplexbildner enthält, wird das Metall über Wechselwirkungen, insbesondere über koordinative bzw. ionische Wechselwirkungen, fixiert.Treatment of the functional group-endowed polymer with the solution containing the metal salt and the complexing agent fixes the metal through interactions, particularly through coordinative and ionic interactions, respectively.
In einer weiteren vorteilhaften Ausführungsform der vorliegenden Erfindung ist das Reduktionsmittel ausgewählt aus der Gruppe, bestehend aus Glucose, Ascorbinsäure, Natriumborhydrid, Natriumdithionit, Natriumsulfit, Natriumformiat, Formaldehyd und Natriumhydrophosphit. Das Reduktionsmittel dient zur Reduktion des ionischen Metalls. Bevorzugt ist das Reduktionsmittel Glucose oder Ascorbinsäure. Glucose bzw. Ascorbinsäure ist ein sehr umweltfreundliches Reduktionsmittel, leicht in der Handhabung, leicht verfügbar und ungiftig. Wenn das Reduktionsmittel Glucose oder Ascorbinsäure ist, wird die Reduktion bevorzugt in Wasser durchgeführt, insbesondere bei Temperaturen zwischen 10° C und 600C, bevorzugt 20° C und 30° C, über eine Zeitdauer zwischen 5 Minuten und 1 Tag, bevorzugt zwischen 30 Minuten und 1 Stunde. Insbesondere bei dem Einsatz von Glucose wird das Reduktionsmittel bevorzugt in Form einer wässrigen Lösung mit einer Konzentration von 1 ,25 bis 5 g/l und einem pH-Wert im Bereich von 7 bis 12, bevorzugt, 8 bis 10,5,
eingesetzt. Der pH-Wert der Reduktionsmittel-haltigen Lösung kann beispielsweise mittels der Zugabe von Ammoniak eingestellt werden. Wenn das Reduktionsmittel Natriumborhydrid ist, wird die Reduktion bevorzugt in Ethanol durchgeführt, insbesondere bei Temperaturen zwischen 100C und 500C, bevorzugt 20° C und 300C, über eine Zeitdauer zwischen 5 Minuten und 2In a further advantageous embodiment of the present invention, the reducing agent is selected from the group consisting of glucose, ascorbic acid, sodium borohydride, sodium dithionite, sodium sulfite, sodium formate, formaldehyde and sodium hydrophosphite. The reducing agent serves to reduce the ionic metal. Preferably, the reducing agent is glucose or ascorbic acid. Glucose or ascorbic acid is a very environmentally friendly reducing agent, easy to handle, readily available and non-toxic. If the reducing agent is glucose or ascorbic acid, the reduction is preferably carried out in water, in particular at temperatures between 10 ° C and 60 0 C, preferably 20 ° C and 30 ° C, over a period between 5 minutes and 1 day, preferably between 30 Minutes and 1 hour. In particular, in the case of the use of glucose, the reducing agent is preferably in the form of an aqueous solution with a concentration of 1, 25 to 5 g / l and a pH in the range of 7 to 12, preferably, 8 to 10.5, used. The pH of the reducing agent-containing solution can be adjusted, for example, by means of the addition of ammonia. When the reducing agent is sodium borohydride, the reduction is preferably carried out in ethanol, in particular at temperatures between 10 0 C and 50 0 C, preferably 20 ° C and 30 0 C, over a period of time between 5 minutes and 2
Stunden, bevorzugt zwischen 15 Minuten und 1 Stunde. Zur Behandlung mit dem Reduktionsmittel wird das Polymer vorteilhaft in die Reduktionsmittel-haltige Lösung eingetaucht bzw. eingelegt und ggf. bewegt. Die Behandlung des Polymers wird bei einem Flottenverhältnis (Verhältnis von der Masse (kg) der Ware zu dem Volumen (I) der Reduktionsmittellösung) von 1 :10 bis 1 :100, bevorzugt 1 :50 bis 1 : 100, durchgeführt. Nach der Behandlung mit der Reduktionsmittel-haltigen Lösung wird das erhaltene metallisierte Polymer in einer vorteilhaften Ausführungsform mit Wasser gewaschen und optional zur Trocknung auf bis zu 150° C erhitzt.Hours, preferably between 15 minutes and 1 hour. For the treatment with the reducing agent, the polymer is advantageously dipped or inserted into the reducing agent-containing solution and optionally agitated. The treatment of the polymer is carried out at a liquor ratio (ratio of the mass (kg) of the product to the volume (I) of the reducing agent solution) of 1:10 to 1: 100, preferably 1:50 to 1: 100. After the treatment with the reducing agent-containing solution, the resulting metallized polymer is washed in an advantageous embodiment with water and optionally heated to drying up to 150 ° C.
Dem erfindungsgemäßen Verfahren wird vorteilhaft ein Polymer unterzogen, das ausgewählt ist aus der Gruppe, bestehend aus Polyamid, Polyester, Polacryl, Polyurethan, Polyolefin, Polyether und deren Mischungen. Das Polymer enthält gegebenenfalls weiterhin einen oder mehrere übliche Hilfs-, Verarbeitungs- oder Zusatzstoffe. Besonders vorteilhaft ist das Polymer ein Polyamid, Polyester oder Polyolefin. Im Sinne der vorliegenden Erfindung umfassen Polyamid, Polyester bzw. Polyolefin sowohl Homopolymere als auch Copolymere. Als Polyamid wird bevorzugt PA 6, PA11 , PA12, PA66, PA46, PA6/6T, PA6/6I, PA1212, PA612, PA 6I, PA 6I/6T, besonders bevorzugt PA 6, PA11 , PA12, PA66 oder PA46, eingesetzt. Als Polyester wird bevorzugt Polyethylenterephthalat,The process according to the invention is advantageously subjected to a polymer which is selected from the group consisting of polyamide, polyester, polacryl, polyurethane, polyolefin, polyether and mixtures thereof. The polymer optionally further contains one or more conventional auxiliaries, processing or additives. The polymer is particularly advantageously a polyamide, polyester or polyolefin. For the purposes of the present invention comprise polyamide, polyester or polyolefin both homopolymers and copolymers. The polyamide PA 6, PA11, PA12, PA66, PA46, PA6 / 6T, PA6 / 6I, PA1212, PA612, PA6I, PA6I / 6T, PA 6, PA11, PA12, PA66 or PA46 is preferably used. As the polyester is preferably polyethylene terephthalate,
Polybutylenterephthalat, Poly-1 ,4-cyclohexandimethylentherephatalat, Polyethylenoxybenzoat oder Poly-1 ,4-cyclohexylidendimethylenterephthalat und deren Mischungen, besonders bevorzugt Polyethylenterephthalat oder Polybutylenterephthalat, eingesetzt. Als Polyolefin wird bevorzugt Polypropylen oder Polyethylen, besonders bevorzugt Polypropylen, eingesetzt. Als Polacryl wird insbesondere Polyacrylnitril eingesetzt. Die üblichen Hilfs-, Verarbeitungsoder Zusatzstoffe schließen Stabilisatoren, Flammschutzmittel, Verarbeitungshilfsmittel, Antistatikmittel, Antioxidationsmittel, Weichmacher,
Farbstoffe, Schlagzähmodifikatoren, Haftungsmodifikatoren, Pigmente, Verstärkungsmittel und/oder Füllstoffe ein, sind aber nicht darauf beschränkt. Bevorzugte Beispiele für die üblichen Hilfs-, Verarbeitungs- oder Zusatzstoffe schließen Kurzglasfasern, Glaskugeln, C-Fasern, Ruß, Kreide, Mika, Talkum, Schwerspat, Glimmer, Wollastonit, Calciumcarbonat, Titandioxid,Polybutylene terephthalate, poly-1, 4-cyclohexandimethylenentherephatalat, polyethyleneoxybenzoate or poly-1, 4-cyclohexylidendimethylenterephthalat and mixtures thereof, particularly preferably polyethylene terephthalate or polybutylene terephthalate used. The polyolefin used is preferably polypropylene or polyethylene, more preferably polypropylene. In particular polyacrylonitrile is used as the acrylic. The usual auxiliary, processing or additives include stabilizers, flame retardants, processing aids, antistatic agents, antioxidants, plasticizers, Dyes, impact modifiers, adhesion modifiers, pigments, reinforcing agents and / or fillers include, but are not limited to. Preferred examples of the usual auxiliaries, processing or additives include short glass fibers, glass beads, carbon fibers, carbon black, chalk, mica, talc, barite, mica, wollastonite, calcium carbonate, titanium dioxide,
Nanocomposites, Graphit, MoS2 , Silikate, Aluminium, Kupfer, Bronze, Stahl, Blei, Zink, Nickel ein, sind aber nicht darauf beschränkt. Weiterhin sind vom Begriff der „Zusatzstoffe" auch Fadenmaterialien aller Art umfasst, die sich textiltechnisch in das Polymer integrieren lassen.Nanocomposites, graphite, MoS 2 , silicates, aluminum, copper, bronze, steel, lead, zinc, nickel, but are not limited thereto. Furthermore, the term "additives" also includes thread materials of all kinds, which can be integrated into the polymer textile technology.
In einer vorteilhaften Ausgestaltung des erfindungsgemäßen Verfahrens wird das Polymer im Anschluss an den Schritt der Behandlung mit einem Reduktionsmittel mit einem Mittel behandelt, das ausgewählt ist aus der Gruppe, bestehend aus Reduktionsmittel, Komplexbildner und Polymer. Die Wirkprinzipien des Mittels sind die Reduktion von eventuell verbliebenen ionischen Metallanteilen im Bereich der Oberfläche des metallisierten Polymers, die Entfernung von eventuell verbliebenen ionischen Metallanteilen von dem metallisierten Polymer mittels Komplexierung bzw. eine Versiegelung des metallisierten Polymers. Diese Wirkstrategien dienen dazu, eine unkontrollierte hohe Metall- bzw. Metallionenabgabe von dem metallisierten Polymer an die Umgebung zu verhindern. Im Sinne der vorliegenden Erfindung dient daher eine derartige Behandlung des metallisierten Polymers als ein Verfahren zur Reduktion von Metallionen, zur Komplexierung von Metallionen bzw. zur Versiegelung einer Metallbeschichtung, um eine zweckorientierte, je nach Applikationsfeld gesteuerte Metallabgabe zu bewirken. Damit werden nicht nur eine höhere Wirtschaftlichkeit, geringere Entsorgungskosten und geringere Umweltschädigung erreicht, sondern auch eine Depotwirkung in der Anwendung erzielt. Eine Depotwirkung in der Anwendung bedeutet, dass eine entsprechend den jeweiligen Richtlinien, Systemvorgaben und Verordnungen zulässige Metallabgabe über einen langen Zeitraum konstant erfolgt. Dadurch wird eine lange Wirkungsdauer und somit eine lange Einsatzfähigkeit des metallisierten Polymers erlangt.
Besonders vorteilhaft ist die Behandlung des metallisierten Polymers mit einem Reduktionsmittel. Als Reduktionsmittel werden vorstehend erwähnte Reduktionsmittel eingesetzt. Die Behandlungsbedingungen sind die gleichen wie vorstehend bereits erwähnt. Im Falle eines erfindungsgemäß besilberten Polymers ist ein bevorzugtes Reduktionsmittel Glucose. Die reduzierende Wirkung wässriger Lösungen von Glucose ist u. a. abhängig von der Glucose- Konzentration und dem pH-abhängigen Redoxpotential, welches von dem pH- Wert linear abhängig. Die Silberabgabe des besilberten Polymers nach der Behandlung mit dem Reduktionsmittel sinkt linear mit steigendem pH-Wert der Reduktionslösung und mit steigendem Oxidationspotential. Das heißt, durch Behandlung des metallisierten Polymers mit dem Reduktionsmittel kann die Metall- bzw. Metallionenabgabe, in diesem Fall die Silber- bzw. Silberionenabgabe, des metallisierten Polymers in eine umgebende Flüssigkeit auf einen bestimmten Wert eingestellt werden.In an advantageous embodiment of the method according to the invention, following the step of treatment with a reducing agent, the polymer is treated with an agent selected from the group consisting of reducing agent, complexing agent and polymer. The active principles of the agent are the reduction of any remaining ionic metal portions in the region of the surface of the metallized polymer, the removal of any remaining ionic metal portions of the metallized polymer by means of complexing or a sealing of the metallized polymer. These action strategies serve to prevent uncontrolled high metal or metal ion release from the metallized polymer to the environment. For the purposes of the present invention, therefore, such a treatment of the metallized polymer serves as a method for the reduction of metal ions, for the complexation of metal ions or for sealing a metal coating to effect a purpose-oriented, depending on the application field controlled metal delivery. Thus, not only a higher economic efficiency, lower disposal costs and lower environmental damage are achieved, but also achieved a depot effect in the application. A depot effect in the application means that a metal delivery permitted in accordance with the respective guidelines, system specifications and regulations is constant over a long period of time. As a result, a long duration of action and thus a long useful life of the metallized polymer is achieved. Particularly advantageous is the treatment of the metallized polymer with a reducing agent. As the reducing agent, reducing agents mentioned above are used. The treatment conditions are the same as mentioned above. In the case of a polymer which has been silvered according to the invention, a preferred reducing agent is glucose. The reducing action of aqueous solutions of glucose depends, inter alia, on the glucose concentration and the pH-dependent redox potential, which depends linearly on the pH. The silver release of the polymerized polymer after treatment with the reducing agent decreases linearly with increasing pH of the reducing solution and with increasing oxidation potential. That is, by treating the metallized polymer with the reducing agent, the metal or metal ion release, in this case the silver ion or silver ion release, of the metallized polymer into a surrounding liquid can be adjusted to a certain value.
In einer anderen bevorzugten Ausführungsform ist das Mittel ein Komplexbildner. Als Komplexbildner wird ein vorstehend erwähnter Komplexbildner eingesetzt. Das metallisierte Polymer wird mit dem Komplexbildner gespült, der in wässriger Lösung vorliegen kann. Anschließend wird das behandelte Polymer gegebenenfalls mit Wasser gewaschen und gegebenenfalls bei einer Temperatur von bis zu 1400C getrocknet.In another preferred embodiment, the agent is a complexing agent. The complexing agent used is a chelating agent mentioned above. The metallized polymer is rinsed with the complexing agent, which may be in aqueous solution. Subsequently, the treated polymer is optionally washed with water and optionally dried at a temperature of up to 140 0 C.
In einer anderen bevorzugten Ausführungsform ist das Mittel ein Polymer. Das Polymer ist bevorzugt ausgewählt aus der Gruppe, bestehend aus Polyurethan, Polyacrylat und Hochveredelungsausrüstung.In another preferred embodiment, the agent is a polymer. The polymer is preferably selected from the group consisting of polyurethane, polyacrylate and finishing equipment.
Durch das erfindungsgemäße Verfahren wird ein metallisiertes Polymer erhalten. Insbesondere wird mittels des erfindungsgemäßen Verfahrens ein besilbertes, bekupfertes oder benickeltes Polymer erhalten. Besonders bevorzugt wird mittels des erfindungsgemäßen Verfahrens ein besilbertesBy the method according to the invention a metallized polymer is obtained. In particular, a besilfertes, bekupfertes or benickeltes polymer is obtained by the method according to the invention. Particularly preferred is a besilbertes by the method according to the invention
Polymer erhalten. Im Sinne der vorliegenden Erfindung kann das metallisierte Polymer ein ganzflächig oder teilflächig metallisiertes Polymer sein.
Das durch das erfindungsgemäße Verfahren erhaltene metallisierte Polymer ist vorteilhaft als ein Garn, eine Faser, ein Filament, ein Gewebe, ein Gestrick, ein Geflecht, ein Gewirke oder ein Vlies ausgebildet. Vorteilhaft ist das durch das erfindungsgemäße Verfahren erhaltene metallisierte Polymer eine Faser. Es eignet sich dann insbesondere zur Herstellung von Strümpfen und Kleidung. In einer anderen vorteilhaften Ausgestaltung der vorliegenden Erfindung ist das erhaltene metallisierte Polymer ein Gewirke, insbesondere ein Abstandsgewirke. Das Abstandsgewirke ist insbesondere zur antimikrobiellen Behandlung von Flüssigkeit in Flüssigkeit-führenden Systemen und Einlegesohlen geeignet.Obtained polymer. For the purposes of the present invention, the metallized polymer may be a full-area or partially metallized polymer. The metallized polymer obtained by the process according to the invention is advantageously in the form of a yarn, a fiber, a filament, a woven fabric, a knitted fabric, a braid, a knitted fabric or a fleece. Advantageously, the metallized polymer obtained by the process according to the invention is a fiber. It is then particularly suitable for the production of stockings and clothing. In another advantageous embodiment of the present invention, the resulting metallized polymer is a knitted fabric, in particular a knitted spacer fabric. The spacer fabric is particularly useful for antimicrobial treatment of fluid in fluid-carrying systems and insoles.
Die vorliegende Erfindung betrifft ebenfalls ein beschichtetes Polymer, das ein Polymer umfasst, das eine Schicht aus einem Additionsprodukt aus einer Verbindung, die mindestens eine Amingruppe aufweist, und einer Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, und eine Schicht aus mindestens einem Metall aufweist, das ausgewählt ist aus der Gruppe, bestehend aus Silber, Kupfer und Nickel. Mittels der Schicht aus dem Additionsprodukt haftet die Metallschicht hervorragend an dem metallisierten Polymer.The present invention also relates to a coated polymer comprising a polymer comprising a layer of an addition product of a compound having at least one amine group and a compound having at least one functional group which is suitable with the amine group an addition reaction and having a layer of at least one metal selected from the group consisting of silver, copper and nickel. By means of the layer of the addition product, the metal layer adheres excellently to the metallized polymer.
Bevorzugt umfasst das beschichtete Polymer, ein Polymer, das eine Schicht aus Harnstoff und eine Schicht aus Silber aufweist. Der Harnstoff ist bevorzugt durch eine Additionsreaktion von mindestens einer Verbindung, die mindestens eine Amingruppe aufweist, mit mindestens einer Verbindung erhalten, die mindestens eine Isocyanatgruppe aufweist.Preferably, the coated polymer comprises a polymer having a layer of urea and a layer of silver. The urea is preferably obtained by an addition reaction of at least one compound having at least one amine group with at least one compound having at least one isocyanate group.
Bevorzugt ist der Harnstoff ein Additionsprodukt aus mindestens einer Verbindung der FormelPreferably, the urea is an addition product of at least one compound of the formula
R1NHR2 (I),R 1 NHR 2 (I),
wobei R1 ausgewählt ist aus der Gruppe, bestehend aus H2N(CH2)W, R3 3Si(CH2)w und H2NC6H4,
R2 ausgewählt ist aus der Gruppe, bestehend aus [(CH2)χNH]y(CH2)zNH2, R3 3Si(CH2)y und H2NC6H4NH(CH2)Y, w eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, x eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, y Null oder eine ganze Zahl von 1 bis 7 ist, bevorzugt Null, 1 oder 2 ist, z eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, und R3 ein verzweigtes oder geradkettiges Alkyl oder -O-Alkyl mit 1 bis 10 Kohlenstoffatomen, bevorzugt mit 1 bis 8 Kohlenstoffatomen, bevorzugter mit 1 oder 2 Kohlenstoffatomen, ist, und einer Verbindung, die ausgewählt ist aus der Gruppe, bestehend auswherein R 1 is selected from the group consisting of H 2 N (CH 2 ) W , R 3 3 Si (CH 2 ) w and H 2 NC 6 H 4 , R 2 is selected from the group consisting of [(CH 2) χNH] y (CH 2 ) z NH 2 , R 3 3 Si (CH 2 ) y and H 2 NC 6 H 4 NH (CH 2 ) Y , w is an integer from 1 to 7, preferably 2 or 3, x is an integer from 1 to 7, preferably 2 or 3, y is zero or an integer from 1 to 7, preferably zero, 1 or 2, z is one is integer from 1 to 7, preferably 2 or 3, and R 3 is a branched or straight-chain alkyl or -O-alkyl of 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms, and a compound selected from the group consisting of
Hexamethylendiisocyanat, Tolylendiisocyanat, Isophorondiisocyanat und 4,4'- Methylenbis(cyclohexylisocyanat).Hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexylisocyanate).
Ein unter Verwendung des erfindungsgemäßen Verfahrens erhaltenes Polymer eignet sich zur antimikrobiellen Behandlung von Flüssigkeiten in einemA polymer obtained using the method of the invention is suitable for the antimicrobial treatment of liquids in one
Flüssigkeit führenden System. Dazu eignet sich insbesondere ein besilbertesLiquid leading system. This is especially a besilbertes
Polymer, da Silber durch seine hervorragende antimikrobielle Wirkung in derPolymer, because of its excellent antimicrobial effect in the silver
Lage ist, insbesondere Bakterien, Pilze und Mikroalgen effektiv zu hemmen.Able to effectively inhibit especially bacteria, fungi and microalgae.
Alternativ wird das metallisierte Polymer zur Herstellung von Strümpfen, Einlegesohlen, Kleidung, Bezugstextilien für Sitzmöbel oder Matratzen verwendet. Auch hier eignet sich insbesondere ein besilbertes Polymer wegen der besonders starken oligodynamischen Eigenschaften.Alternatively, the metallized polymer is used to make stockings, insoles, clothing, upholstery for seating or mattresses. Again, a besilbertes polymer is particularly suitable because of the particularly strong oligodynamic properties.
Das metallisierte Polymer wird insbesondere bei der Behandlung einer Flüssigkeit in Form einer Nutzflüssigkeit oder in Form von Trinkwasser eingesetzt. Diese Flüssigkeiten können in zur umgebenden Atmosphäre hin geschlossenen oder offenen, stagnierenden oder im Kreislauf geführten Systemen in Kraftwerken, industriellen oder gewerblichen Anlagen oder Klimaanlagen vorliegen. In jedem Fall lässt sich die Metall- Elution des erfindungsgemäßen Polymers individuell derart einstellen, dass beispielsweise beim Einsatz zur Behandlung von Flüssigkeit in Form von Trinkwasser unterschiedliche nationale Vorschriften hinsichtlich der maximal zulässigen Metallkonzentration im Trinkwasser eingehalten werden.
Der Begriff der „Nutzflüssigkeit" dient als Oberbegriff für eine Flüssigkeit, die eine oder mehrere Funktionalitäten wie beispielsweise Kühlen, Schmieren, hydraulisch Schalten und Steuern erfüllt oder als Brauch- oder Prozessflüssigkeit verbraucht wird.The metallized polymer is used in particular in the treatment of a liquid in the form of a useful liquid or in the form of drinking water. These fluids may be present in closed or open, stagnant, or recirculating systems in power plants, industrial, commercial, or air conditioning systems. In any case, the metal elution of the polymer according to the invention can be adjusted individually such that, for example, when used for the treatment of liquid in the form of drinking water, different national regulations regarding the maximum permissible metal concentration in drinking water are adhered to. The term "useful liquid" serves as a generic term for a liquid which fulfills one or more functionalities such as, for example, cooling, lubricating, hydraulically switching and controlling, or which is consumed as a process or process fluid.
Eine bevorzugte Verwendung besteht darin, dass die antimikrobielle Behandlung einer Flüssigkeit in einem Flüssigkeit führenden System die Behandlung eines flüssigen Kühlschmierstoffs im Kühlschmierstoff- Kreislauf einer Metall bearbeitenden Anlage umfasst. Derartige Kühlschmierflüssigkeiten werden üblicherweise bei industriellen und gewerblichen Anlagen eingesetzt, die Metalle durch einen Substanzeingriff bearbeiten, beispielsweise durch Drehen, Fräsen oder Bohren. Besonders vorteilhaft ist die Verwendung wenn die Kühlschmierflüssigkeit als Wasser-Öl-Emulsion in einem Kühlschmierflüssigkeitssystem eingesetzt wird. Die Kühlschmierflüssigkeit bleibt dadurch, ohne dass dazu die bisher üblichen Biozide, insbesondere auf Formaldehydbasis, notwendig sind, mikrobiologisch stabil. Dadurch ergeben sich geringere gesundheitliche Belastungen des Bedienpersonals und geringere Kosten durch höhere Standzeiten. Mittels des erfindungsgemäßen Verfahrens kann die Abgabe anti-mikrobiell wirkender Metallbestandteile den Anforderungen entsprechend optimal eingestellt werden.A preferred use is that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid cooling lubricant in the cooling lubricant circuit of a metal-working plant. Such lubricating fluids are commonly used in industrial and commercial plants that process metals by a substance engagement, such as by turning, milling or drilling. Particularly advantageous is the use when the cooling lubricant liquid is used as a water-oil emulsion in a cooling lubricant system. The cooling lubricant remains characterized, without the usual biocides, especially on formaldehyde-based, are necessary microbiologically stable. This results in lower health burdens on operating personnel and lower costs due to longer service life. By means of the method according to the invention, the delivery of antimicrobial metal components can be optimally adjusted according to the requirements.
Eine weitere bevorzugte Verwendung besteht darin, dass die antimikrobielle Behandlung einer Flüssigkeit in einem Flüssigkeit führenden System die Behandlung eines flüssigen Schaltmediums in hydraulischen Schaltkreislauf einer industriellen Anlage umfasst. Auch bei hydraulischen Schaltkreisläufen kommt es vor, dass Biomassewachstum ein Problem darstellt. Dies gilt insbesondere für Kreisläufe mit Bereichen, durch die regelmäßig Material in das Hydraulik- Medium gelangt, das sich als Nahrung für große Mengen an Mikroorganismen eignet. Dies gilt beispielsweise für Anlagen, die mit zellulosehaltigenA further preferred use is that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid switching medium in the hydraulic circuit of an industrial plant. Also in hydraulic circuits it happens that biomass growth is a problem. This applies in particular to circuits with areas through which material is routinely introduced into the hydraulic medium which is suitable for feeding large quantities of microorganisms. This applies, for example, to systems containing cellulose
Materialien Kontakt haben. Gleiches gilt für Materialien mit Naturfasern wie Baumwolle, Leinen, Wolle etc. Das Verfahren ist daher besonders vorteilhaft dort einsetzbar, wo die industrielle oder gewerbliche Anlage als
Papierproduktions- und/oder Verarbeitungsanlage oder als Anlage zur Herstellung und/oder Verarbeitung von Textilen ausgebildet ist. Wie vorangehend erwähnt ist auch hier die bedarfsgerechte Einstellung der Elution oligodynamisch aktiver Metallionen gegeben.Materials have contact. The same applies to materials with natural fibers such as cotton, linen, wool, etc. The method is therefore particularly advantageous where the industrial or commercial plant as Paper production and / or processing plant or as a plant for the production and / or processing of textiles is formed. As mentioned above, the need-based adjustment of the elution of oligodynamically active metal ions is also given here.
Eine weitere bevorzugte Verwendung sieht vor, dass die antimikrobielle Behandlung einer Flüssigkeit in einem Flüssigkeit führenden System in einer Waschanlage für ein Waschgut die Behandlung von zurückbehaltenem Waschgut- Spülwasser umfasst. Dadurch ist es möglich, das zurückbehaltene Waschgut- Spülwasser in einem Reservoir aufzubewahren, ohne dass man Gefahr läuft, dass dieses Wasser aufgrund mikrobieller Aktivität auf Dauer unbrauchbar wird. Dies gilt immer dann besonders, wenn beispielsweise beim Spülen des Waschgutes Substanzen ausgewaschen werden, die eine gute Nahrungsgrundlage für Mikroorganismen darstellen. Dies insbesondere beim Waschen von Naturfaser- Textilien der Fall. Mit besonderem Vorteil ist daher vorgesehen, dass das behandelte Waschgut-Spülwasser als Waschwasser für einen neu beginnenden Waschgang der Waschanlage eingesetzt werden wird. Dadurch, dass z.B. bei Waschmaschinen das Spülwasser des letzten Spülganges für die Verwendung als erstes Waschwasser in einem neuen Waschgang aufbewahrt wird, kann auf einfache Weise eine weitere Reduzierung des Wasserverbrauches von Waschmaschinen realisiert werden. Dieser Effekt lässt sich auf weitere Waschanlagen und Waschverfahren für unterschiedliche Waschgüter übertragen.A further preferred use provides that the antimicrobial treatment of a liquid in a liquid-conducting system in a laundry washing plant comprises the treatment of retained wash rinse water. This makes it possible to store the retained Waschgut- rinse water in a reservoir, without running the risk that this water due to microbial activity in the long term unusable. This is especially true when, for example, when rinsing the laundry substances are washed out, which represent a good food base for microorganisms. This is the case in particular when washing natural fiber textiles. With particular advantage is therefore provided that the treated wash rinse water will be used as wash water for a new beginning wash cycle of the car wash. By having e.g. in washing machines, the rinse water of the last rinse cycle for use as the first wash water is stored in a new wash, a further reduction of water consumption of washing machines can be realized in a simple manner. This effect can be transferred to other washing systems and washing processes for different laundry items.
Eine weitere bevorzugte Verwendung sieht vor, dass die antimikrobielle Behandlung einer Flüssigkeit in einem Flüssigkeit führenden System in einer medizintechnischen Vorrichtung die Behandlung keimfreien Nutzwassers umfasst. Dabei ist es regelmäßig erforderlich, hohe Anforderungen im Hinblick an eine dauerhafte Keimfreiheit des Wassers und eines damit in Kontakt kommenden Leitungssystems zu gewährleisten. Dies kann auf einfache und zuverlässige Weise durch die Verwendung eines dreidimensionalen Fadensystems mit oligodynamischer Aktivität gewährleistet werden.
Die vorliegende Erfindung wird nun unter Bezugnahme auf ein Ausführungsbeispiel detaillierter erläutert. Die vorliegende Erfindung ist jedoch nicht auf das Ausführungsbeispiel beschränkt.A further preferred use provides that the antimicrobial treatment of a liquid in a fluid-carrying system in a medical device comprises the treatment of germ-free working water. It is regularly necessary to ensure high requirements with regard to a permanent sterility of the water and a thus coming in contact with the pipeline system. This can be ensured in a simple and reliable manner by the use of a three-dimensional suture system with oligodynamic activity. The present invention will now be explained in more detail with reference to an embodiment. However, the present invention is not limited to the embodiment.
Beispielexample
Ein Abstandsgewirke aus Polyester wurde 1 Minute lang in Hexamethylendiisocyanat (20% in Wasser) und anschließend 3 Stunden lang in Bis(3-aminopropyl)amin getaucht. Der so behandelte Polyester wurde 1 Tag lang bei 200C trocknen gelassen. Der so behandelte Polyester wurde in einer Mischung aus wässriger Silbernitrat-Lösung (5%) und Ammoniak-Lösung (25%) bei einem Flottenverhältnis von 1 :1 3 Stunden lang bei 500C unter Rühren erhitzt. Der so behandelte Polyester wurde in eine wässrige Ascorbinsäure-Lösung (10 %) bei einem pH = 11 gelegt. Durch eine Nachbehandlung des so besilberten Polyesters mit einer Mischung aus wässriger Silbernitrat-Lösung (5%) und Ammoniak-Lösung (25%) über 10 Minuten unter Rühren konnte der Versilberungsgrad weiterhin erhöht werden.
A polyester spacer fabric was immersed in hexamethylene diisocyanate (20% in water) for 1 minute and then in bis (3-aminopropyl) amine for 3 hours. The thus-treated polyester was allowed to dry at 20 ° C. for 1 day. The thus treated polyester was heated in a mixture of aqueous silver nitrate solution (5%) and ammonia solution (25%) at a liquor ratio of 1: 1 for 3 hours at 50 0 C with stirring. The thus-treated polyester was placed in an aqueous solution of ascorbic acid (10%) at pH = 11. By aftertreatment of the so besilberten polyester with a mixture of aqueous silver nitrate solution (5%) and ammonia solution (25%) over 10 minutes with stirring, the degree of silvering could be further increased.
Claims
1 . Verfahren zur Metallisierung eines Polymers, bei dem das Polymer nacheinander • mit mindestens einer Verbindung behandelt wird, die mindestens eine1 . Process for metallizing a polymer, in which the polymer is treated successively with at least one compound containing at least one
Amingruppe aufweist,Has amine group,
• mit einer Verbindung behandelt wird, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, • mit einer Lösung behandelt wird, die mindestens ein Metallsalz, das ausgewählt ist aus der Gruppe bestehend aus einem Silbersalz, einem Kupfersalz und einem Nickelsalz, und einen Komplexbildner enthält, und• treated with a compound having at least one functional group capable of performing an addition reaction with the amine group, • treated with a solution containing at least one metal salt selected from the group consisting of a silver salt, a copper salt and a nickel salt, and containing a complexing agent, and
• mit mindestens einem Reduktionsmittel behandelt wird.• treated with at least one reducing agent.
2. Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, dass der Schritt der Behandlung mit einer Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, vor dem Schritt der Behandlung mit einer Verbindung ausgeführt wird, die mindestens eine Amingruppe aufweist.A method according to claim 1, characterized in that the step of treatment with a compound having at least one functional group capable of performing an addition reaction with the amine group is carried out prior to the step of treatment with a compound which is at least has an amine group.
3. Verfahren gemäß einem der vorangehenden Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die mindestens eine Verbindung, die mindestens eine Amingruppe aufweist, eine Verbindung der Formel3. The method according to any one of the preceding claims 1 or 2, characterized in that the at least one compound having at least one amine group, a compound of formula
R1NHR2 (I)R 1 NHR 2 (I)
ist, wobei R1 ausgewählt ist aus der Gruppe, bestehend aus H2N(CH2)W,wherein R 1 is selected from the group consisting of H 2 N (CH 2 ) W ,
R3 3Si(CH2)w und H2NC6H4,R 3 3 Si (CH 2 ) w and H 2 NC 6 H 4 ,
R2 ausgewählt ist aus der Gruppe, bestehend aus [(CH2)xNH]y(CH2)zNH2, R 53J 3Si(CH2)z und H2NC6H4NH(CH2) Z) w eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, x eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, y Null oder eine ganze Zahl von 1 bis 7 ist, bevorzugt Null, 1 oder 2 ist, z eine ganze Zahl von 1 bis 7, bevorzugt 2 oder 3, ist, R3 ein verzweigtes oder geradkettiges Alkyl oder -O-Alkyl mit 1 bis 10 Kohlenstoffatomen, bevorzugt mit 1 bis 8 Kohlenstoffatomen, bevorzugter mit 1 oder 2 Kohlenstoffatomen, ist.R 2 is selected from the group consisting of [(CH 2 ) x NH] y (CH 2 ) z NH 2 , R 5 3 J 3 Si (CH 2 ) z and H 2 NC 6 H 4 NH (CH 2 ) Z) w is an integer from 1 to 7, preferably 2 or 3, x is an integer from 1 to 7, preferably 2 or 3, y is zero or an integer from 1 to 7, preferably zero, 1 or 2, z is an integer of 1 to 7, preferably 2 or 3, R 3 is a branched or straight chain alkyl or -O-alkyl of 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.
4. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Verbindung, die mindestens eine Amingruppe aufweist, ausgewählt ist aus der Gruppe, bestehend aus Bis(3- aminopropyl)amin, N,N'-Bis(2-aminoethyl)-1 ,3-propandiamin, Triethylentetramin, Tetraethylenpentamin, Bis[3-4. The method according to any one of the preceding claims 1 to 3, characterized in that the compound having at least one amine group is selected from the group consisting of bis (3-aminopropyl) amine, N, N'-bis (2- aminoethyl) -1,3-propanediamine, triethylenetetramine, tetraethylenepentamine, bis [3-
(trimethoxysilyl)propyl]amin und Bis[3-(trimethylsilyl)propyl]amin.(trimethoxysilyl) propyl] amine and bis [3- (trimethylsilyl) propyl] amine.
5. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die mindestens eine Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine5. The method according to any one of the preceding claims 1 to 4, characterized in that the at least one compound having at least one functional group which is suitable with the amine group a
Additionsreaktion durchzuführen, mindestens eine Isocyanatgruppe aufweist, bevorzugt eine Verbindung mit zwei Isocyanatgruppen darstellt.To perform addition reaction, at least one isocyanate group, preferably represents a compound having two isocyanate groups.
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass die Verbindung, die mindestens eine Isocyanatgruppe aufweist, ausgewählt ist aus der6. The method according to claim 5, characterized in that the compound having at least one isocyanate group is selected from
Gruppe, bestehend aus Hexamethylendiisocyanat, Tolylendiisocyanat, Isophorondiisocyanat und 4,4'-Methylenbis(cyclohexyl)isocyanat, wobei Hexamethylendiisocyanat besonders bevorzugt ist.A group consisting of hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl) isocyanate, with hexamethylene diisocyanate being particularly preferred.
7. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die mindestens eine Verbindung, die mindestens eine funktionelle Gruppe aufweist, die geeignet ist, mit der Amingruppe eine Additionsreaktion durchzuführen, mindestens eine Epoxidgruppe aufweist, wobei die Verbindung mit mindestens einer Epoxidgruppe bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Propylenoxid, Styroloxid, 2,3-7. The method according to any one of the preceding claims 1 to 4, characterized in that the at least one compound having at least one functional group which is suitable to perform an addition reaction with the amine group, at least one epoxy group, wherein the compound with at least one Epoxy group is preferably selected from the group consisting of propylene oxide, styrene oxide, 2,3-
Dimethyl-2,3-epoxybutan, 4-Vinyl-1 -cyclohexen-1 ,2-epoxid, Limonen-1 ,2- epoxid und Epoxidharz, insbesondere Epoxidharz vom Bisphenolglycidether- Typ. Dimethyl-2,3-epoxybutane, 4-vinyl-1-cyclohexene-1, 2-epoxide, limonene-1, 2-epoxide and epoxy resin, especially Bisphenolglycidether- type epoxy resin.
8. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Metallsalz ausgewählt ist aus der Gruppe, bestehend aus Silberhalogenid, Silbersulfat, Silbernitrat, Kupferhalogenid, Kupfersulfat, Kupfernitrat, Kupferacetat, Nickelhalogenid, Nickelsulfat,8. The method according to any one of the preceding claims 1 to 7, characterized in that the metal salt is selected from the group consisting of silver halide, silver sulfate, silver nitrate, copper halide, copper sulfate, copper nitrate, copper acetate, nickel halide, nickel sulfate,
Nickelnitrat und Nickelacetat, dass das Metallsalz bevorzugt Silbernitrat, Silberchlorid oder Silbersulfat ist.Nickel nitrate and nickel acetate, that the metal salt is preferably silver nitrate, silver chloride or silver sulfate.
9. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Komplexbildner ausgewählt ist aus der Gruppe, bestehend aus Ammoniak, Ethylendiamin, Triethanolamin, Ethanolamin, 1 ,3- Diaminopropan, Natriumthiosulfat, Thioisocyanat, Glycerol, Natriumtartrat, Natriumkaliumtartrat und Natriumeitrat.9. The method according to any one of the preceding claims 1 to 8, characterized in that the complexing agent is selected from the group consisting of ammonia, ethylenediamine, triethanolamine, ethanolamine, 1, 3-diaminopropane, sodium thiosulfate, thioisocyanate, glycerol, sodium tartrate, sodium potassium tartrate and sodium citrate.
10. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Reduktionsmittel ausgewählt ist aus der Gruppe, bestehend aus Glucose, Ascorbinsäure, Natriumborhydrid, Natriumdithionit, Natriumsulfit, Natriumformiat, Formaldehyd und Natriumhydrophosphit.10. The method according to any one of the preceding claims 1 to 9, characterized in that the reducing agent is selected from the group consisting of glucose, ascorbic acid, sodium borohydride, sodium dithionite, sodium sulfite, sodium formate, formaldehyde and sodium hydrophosphite.
11. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das Polymer ausgewählt ist aus der Gruppe, bestehend aus Polyamid, Polyester, Polacryl, Polyurethan, Polyolefin, Polyether und deren Mischungen.11. The method according to any one of the preceding claims 1 to 10, characterized in that the polymer is selected from the group consisting of polyamide, polyester, polacrylic, polyurethane, polyolefin, polyether and mixtures thereof.
12. Verfahren gemäß einem der vorangehenden Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass das Polymer nach der Behandlung mit dem Reduktionsmittel mit einem Mittel behandelt wird, das ausgewählt ist aus der Gruppe, bestehend aus Reduktionsmittel, Komplexbildner und Polymer.12. The method according to any one of the preceding claims 1 to 11, characterized in that the polymer is treated after the treatment with the reducing agent with an agent which is selected from the group consisting of reducing agent, complexing agent and polymer.
13. Metallisiertes Polymer, erhalten nach einem der Verfahren gemäß den Ansprüchen 1 bis 12. 13. Metallized polymer, obtained according to one of the methods according to claims 1 to 12.
14. Metallisiertes Polymer gemäß Anspruch 13, dadurch gekennzeichnet, dass es als ein Garn, eine Faser, ein Filament, ein Gewebe, ein Gestrick, ein Geflecht, ein Gewirke oder ein Vlies ausgebildet ist.14. A metallized polymer according to claim 13, characterized in that it is formed as a yarn, a fiber, a filament, a woven fabric, a knitted fabric, a braid, a knitted fabric or a fleece.
15. Verwendung eines Polymers gemäß einem der Ansprüche 13 und 14, zur antimikrobiellen Behandlung von Flüssigkeit in Flüssigkeit-führenden Systemen oder zur Herstellung von Strümpfen, Einlegesohlen, Kleidung, Bezugstextilien für Sitzmöbel oder Matratzen. 15. Use of a polymer according to any one of claims 13 and 14, for the antimicrobial treatment of liquid in liquid-conducting systems or for the production of stockings, insoles, clothing, upholstery for seating or mattresses.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007056599A DE102007056599A1 (en) | 2007-11-21 | 2007-11-21 | Process for metallizing a polymer |
| PCT/EP2008/065968 WO2009065924A1 (en) | 2007-11-21 | 2008-11-21 | Method for metallising a polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2217757A1 true EP2217757A1 (en) | 2010-08-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08853073A Withdrawn EP2217757A1 (en) | 2007-11-21 | 2008-11-21 | Method for metallising a polymer |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20100261865A1 (en) |
| EP (1) | EP2217757A1 (en) |
| JP (1) | JP2011504210A (en) |
| KR (1) | KR20100113062A (en) |
| CN (1) | CN101918637A (en) |
| AU (1) | AU2008327821A1 (en) |
| CA (1) | CA2706511A1 (en) |
| DE (1) | DE102007056599A1 (en) |
| IL (1) | IL205894A0 (en) |
| WO (1) | WO2009065924A1 (en) |
| ZA (1) | ZA201004237B (en) |
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|---|---|---|---|---|
| DE102010036535A1 (en) * | 2010-07-21 | 2012-01-26 | Saint-Gobain Isover G+H Ag | Method for metallizing mineral fibers and use thereof |
| DE202011108086U1 (en) | 2011-11-21 | 2012-01-23 | Martin Bergmann Umwelttechnik | Arrangement for sanitizing water in a swimming pool system or swimming or bathing area |
| DE102015221750B4 (en) | 2015-11-05 | 2019-10-31 | WM aquatec GmbH & Co.KG | Coated particulate polymeric material, methods of making the coated particulate polymeric material, and use of the coated particulate polymeric material |
| US10683400B1 (en) * | 2015-12-18 | 2020-06-16 | Hrl Laboratories, Llc | Chemically or environmentally responsive polymers with reversible mechanical properties |
| CN105714552B (en) * | 2016-04-07 | 2018-01-30 | 中原工学院 | A kind of preparation method of copper sulfide/terylene composite conducting fiber |
| CN112553880B (en) * | 2020-11-24 | 2022-03-01 | 东华大学 | Method for depositing metal oxide on surface of limited-time protective product based on polyolefin non-woven fabric and protective product prepared by method |
| KR102554851B1 (en) * | 2022-08-01 | 2023-07-13 | (주)스패로우 | Recycled polyester fiber for air-mat sheet, air-mat sheet using the same and method for fabricating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799794A (en) * | 1969-09-23 | 1974-03-26 | Hooker Chemical Corp | Process of metal plating |
| DE3419755A1 (en) | 1984-05-26 | 1985-11-28 | Bayer Ag, 5090 Leverkusen | Chemical silvering bath |
| JPS6155263A (en) | 1984-08-20 | 1986-03-19 | 株式会社 高瀬染工場 | Improved metallization of polyester fiber-containing fiber material |
| IT1217328B (en) * | 1988-02-01 | 1990-03-22 | Donegani Guido Ist | PROCESS FOR THE METALLIZATION OF FIBROUS MATERIALS |
| DE3814506A1 (en) * | 1988-04-29 | 1989-11-09 | Bayer Ag | METHOD FOR METALLIZING SUBSTRATE SURFACES |
| AUPN705195A0 (en) * | 1995-12-08 | 1996-01-11 | Cardiac Crc Nominees Pty Limited | Electroless deposition of metallic coatings on non-conducting substrates |
| GB9903842D0 (en) | 1999-02-20 | 1999-04-14 | Arcasorb Technolgy Limited | Substrates and substrate treatment process |
| WO2006052548A1 (en) | 2004-11-05 | 2006-05-18 | University Of Maryland Biotechnology Institute | Metal-enhanced fluorescence from plastic substrates |
| DE102005020889A1 (en) * | 2005-05-04 | 2006-11-09 | Fritz Blanke Gmbh & Co.Kg | Antimicrobial finishing of textiles, particularly fabrics, by treatment first with bath containing silver particles and then with bath containing aqueous binder |
| DE102006055763B4 (en) * | 2006-11-21 | 2011-06-22 | Militz, Detlef, 15366 | Process for metallizing polyester, metallized polyester and its use |
-
2007
- 2007-11-21 DE DE102007056599A patent/DE102007056599A1/en not_active Withdrawn
-
2008
- 2008-11-21 CA CA2706511A patent/CA2706511A1/en not_active Abandoned
- 2008-11-21 EP EP08853073A patent/EP2217757A1/en not_active Withdrawn
- 2008-11-21 CN CN2008801208033A patent/CN101918637A/en active Pending
- 2008-11-21 US US12/743,902 patent/US20100261865A1/en not_active Abandoned
- 2008-11-21 JP JP2010534489A patent/JP2011504210A/en active Pending
- 2008-11-21 WO PCT/EP2008/065968 patent/WO2009065924A1/en active Application Filing
- 2008-11-21 KR KR1020107013322A patent/KR20100113062A/en not_active Application Discontinuation
- 2008-11-21 AU AU2008327821A patent/AU2008327821A1/en not_active Abandoned
-
2010
- 2010-05-20 IL IL205894A patent/IL205894A0/en unknown
- 2010-06-15 ZA ZA2010/04237A patent/ZA201004237B/en unknown
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| Title |
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| See references of WO2009065924A1 * |
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| AU2008327821A1 (en) | 2009-05-28 |
| US20100261865A1 (en) | 2010-10-14 |
| CN101918637A (en) | 2010-12-15 |
| KR20100113062A (en) | 2010-10-20 |
| CA2706511A1 (en) | 2009-05-28 |
| WO2009065924A1 (en) | 2009-05-28 |
| DE102007056599A1 (en) | 2009-05-28 |
| JP2011504210A (en) | 2011-02-03 |
| ZA201004237B (en) | 2011-05-25 |
| IL205894A0 (en) | 2010-11-30 |
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