EP3221491A1 - Multi-layered elastomer article and method for making the same - Google Patents
Multi-layered elastomer article and method for making the sameInfo
- Publication number
- EP3221491A1 EP3221491A1 EP15795206.0A EP15795206A EP3221491A1 EP 3221491 A1 EP3221491 A1 EP 3221491A1 EP 15795206 A EP15795206 A EP 15795206A EP 3221491 A1 EP3221491 A1 EP 3221491A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- per
- groups
- group
- compound
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000000806 elastomer Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 238000001465 metallisation Methods 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001033 ether group Chemical group 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical group 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 39
- 239000010410 layer Substances 0.000 description 35
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 23
- -1 ethylene-chloro-trifluoro-ethylene Chemical group 0.000 description 18
- 229910052740 iodine Inorganic materials 0.000 description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 239000011630 iodine Substances 0.000 description 16
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 229920002379 silicone rubber Polymers 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920006126 semicrystalline polymer Polymers 0.000 description 4
- 238000005211 surface analysis Methods 0.000 description 4
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 4
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical class FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 3
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920000260 silastic Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000005102 attenuated total reflection Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002346 iodo group Chemical group I* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- TUAPLLGBMYGPST-UHFFFAOYSA-N 2,5-dimethyl-2,5-bis(2-methylbutan-2-ylperoxy)hexane Chemical compound CCC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)CC TUAPLLGBMYGPST-UHFFFAOYSA-N 0.000 description 1
- LNGPDTPLWLXXEE-UHFFFAOYSA-N 3-(5,5-diethyl-3,4-dimethylheptan-3-yl)peroxy-5,5-diethyl-3,4-dimethylheptane Chemical compound CCC(CC)(CC)C(C)C(C)(CC)OOC(C)(CC)C(C)C(CC)(CC)CC LNGPDTPLWLXXEE-UHFFFAOYSA-N 0.000 description 1
- WBLRBQCSSBJIPF-UHFFFAOYSA-N 3-bromo-1,1,2,3-tetrafluorobut-1-ene Chemical compound CC(F)(Br)C(F)=C(F)F WBLRBQCSSBJIPF-UHFFFAOYSA-N 0.000 description 1
- FGHPXAKHUFZDRY-UHFFFAOYSA-N 3-ethyl-3-(3-ethylpentan-3-ylperoxy)pentane Chemical compound CCC(CC)(CC)OOC(CC)(CC)CC FGHPXAKHUFZDRY-UHFFFAOYSA-N 0.000 description 1
- VQGABIYDHNEEEC-UHFFFAOYSA-N 3-methyl-3-(3-methylpentan-3-ylperoxy)pentane Chemical compound CCC(C)(CC)OOC(C)(CC)CC VQGABIYDHNEEEC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical class PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HCRGWALAALVWIL-UHFFFAOYSA-N bis(4-tert-butylperoxy-4-methylpentan-2-yl) carbonate Chemical compound CC(C)(C)OOC(C)(C)CC(C)OC(=O)OC(C)CC(C)(C)OOC(C)(C)C HCRGWALAALVWIL-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
-
- 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
- C23C18/1675—Process conditions
- C23C18/1687—Process conditions with ionic liquid
-
- 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
-
- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
-
- 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
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
-
- 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
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Definitions
- the present invention relates to a multi-layered elastomer article and to a method for its manufacturing.
- (Per)fluoroelastomers are known to be relatively chemically inert, thermally stable polymers, owing primarily to the strength of the carbon-fluorine bonds present in the molecule.
- the (per)fluoroelastomers are desirable in many applications which require elastomeric materials able to provide high performances, such as withstanding to high temperatures.
- WO WO 2013/101822 3M INNOVATIVE PROPERTIES CO. discloses a fluoroelastomer material bearing a conductive metal overlayer bound to said fluoroelastomer material through a thin layer of titanium.
- the method for making said material comprises the steps of (a) providing a fluoroelastomer material, optionally (d) exposure of the fluoroelastomer to oxygen plasma, (b) applying a layer of titanium metal to the fluoroelastomer material by a vapour coating method, (c) applying a metal overlayer to the fluoroelastomer material by a vapour coating method, and optionally (e) electroplating the fluoroelastomer.
- the high performing polymers coated with metal layers using conventional approaches can suffer of problems such as easy peeling of the metallic coating from the substrate and poor durability of the coating.
- WO WO 2014/154733 SOLVAY SPECIALTY POLYMERS S.P.A. discloses a multilayer mirror assembly made of ethylene-chloro-trifluoro-ethylene (ECTFE), a semi-crystalline partially fluorinated polymer, treated by a radio-frequency plasma discharge process, and then coated with metallic nickel by electroless plating.
- ECTFE ethylene-chloro-trifluoro-ethylene
- semi-crystalline polymers such as ECTFE, and elastomers have different chemical-physical properties and are used in different applications. Also, semi-crystalline polymers do not undergo to elongation and, hence, they are not affected by the problems typically encountered when using elastomers.
- defects in the metallic layer applied on the surface of the elastomer can become particularly evident when the elastomer undergoes to elongation, resulting in a loss of continuity in the metal layer and consequent decrease or loss of the properties imparted by the metal coating, such as for example barrier to fluids and thermal/electrical conductivity.
- FR 2139998 DR. ING. MAX SCHLOTTER discloses plastics and articles made therefrom which are metal plated by conditioning their surface by a treatment with sulfur trioxide vapor or a sulfur trioxide containing atmosphere.
- Example 23 discloses the treatment of a soft rubber plate, which is first exposed to the sulfur trioxide vapor phase, then treated with an activating solution, a reducing solution and then chemically nickel plated. Then, the metal layer is reinforced by electroplating with a copper deposit. The authors concluded that “when heating the plates after copper plating to 80°C for two hours, the adherence of the copper layer to the plate is such that the metal layer does not separate from the rubber plate but that the rubber plate itself becomes torn”.
- US 2009/0017319 A FRAMATOME CONNECTORS INT. discloses a process for metallizing support media made from plastic material, particularly from high temperature plastic material such as those for electronic industry, notably semi-crystalline polymer or liquid crystal polymers or polybutylene terephthalate (PBT) or polyphenylene sulphide (PPS) or syndiotactic polystyrene (SPS).
- PBT polybutylene terephthalate
- PPS polyphenylene sulphide
- SPS syndiotactic polystyrene
- the Applicant faced the problem to provide an elastomer article having high adhesion to a metallic layer, such that defects in the metallic layer are avoided or at least minimized even after the elastomer has undergone to elongation.
- the present invention relates to a multi-layered article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S)] comprising: - nitrogen-containing groups [groups (N)] and - at least one layer [layer (L1)] adhered to said surface (S) comprising at least one metal compound [compound (M)].
- said groups (N) are grafted onto said surface (S).
- chemical bonds is intended to indicate any type of chemical bond, such as for example covalent bond, ionic bond, dipolar (or coordinate) bond, between at least part of groups (N) grafted on the surface of the elastomer and compound (M).
- the article according to the present invention comprising said layer (L1) adhered to said surface (S) provides electrical and thermal conductivity and a barrier to gases and liquids, and can withstand extreme environmental conditions due to chemical resistance, abrasion resistance and wear resistance, while maintaining its typical flexibility and mechanical properties.
- the present invention relates to a method for manufacturing a multi-layered article, said method comprising the steps of: (i) providing an article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S-1)]; (ii) forming nitrogen-containing groups [groups (N)] on said at least one surface (S-1) so as to provide an elastomer article having at least one nitrogen-containing surface [surface (S-2)]; (iii) contacting said at least one surface (S-2) with a first composition [composition (C1)] comprising at least one metallization catalyst, so as to provide an article having at least one surface [surface (S-3)] containing groups (N) and at least one metallization catalyst; and (iv) contacting said at least one surface (S-3) with a second composition [composition (C2)] containing at least one metal compound [compound (M1)], so as to provide
- the above method comprises after step (iv), step (v) of applying a third composition [composition (C3)] containing at least one metal compound [compound (M2)] onto said surface (S).
- a third composition [composition (C3)] containing at least one metal compound [compound (M2)] onto said surface (S).
- said multi-layered article is in the form of a film or a shaped article.
- the thickness of said film is not particularly limited.
- said film can have a thickness of between 0.5 mm and 10 mm.
- elastomer indicates amorphous polymers or polymers having a low degree of crystallinity (crystalline phase less than 20% by volume) and a glass transition temperature value (T g ), measured according to ASTM D3418, below room temperature. More preferably, the elastomer according to the present invention has a T g below 5°C, even more preferably below 0°C.
- said elastomer comprises recurring units derived from at least one at least one (per)fluorinated monomer and/or at least one hydrogenated monomer.
- said monomers are free of nitrogen atoms.
- the expression “at least one (per)fluorinated monomer” it is hereby intended to denote a polymer comprising recurring units derived from one or more than one (per)fluorinated monomers.
- the expression “(per)fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that it denote both one or more than one fluorinated monomers as defined above.
- the prefix "(per)” in the expression “(per)fluorinated monomer” and in the term “(per)fluoroelastomer” means that the monomer or the elastomer can be fully or partially fluorinated.
- At least one hydrogenated monomer is intended to mean that the polymer may comprise recurring units derived from one or more than one hydrogenated monomers.
- hydrophilic monomer it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
- Non limitative examples of suitable hydrogenated monomers include, notably, non-fluorinated monomers such as C 2 -C 8 non-fluorinated olefins (OI), in particular C 2 -C 8 non-fluorinated alpha-olefins (OI), including ethylene, propylene, 1-butene; diene monomers; vinyl monomers such as vinyl acetate and methyl-vinyl ether (MVE); acrylic monomers, like methyl methacrylate, butyl acrylate; styrene monomers, like styrene and p ⁇ methylstyrene; and silicon-containing monomers.
- non-fluorinated monomers such as C 2 -C 8 non-fluorinated olefins (OI), in particular C 2 -C 8 non-fluorinated alpha-olefins (OI), including ethylene, propylene, 1-butene; diene monomers; vinyl monomers such as vinyl a
- said elastomer is a (per)fluoro-elastomer or a silicone elastomer.
- said (per)fluoro-elastomer has a T g of less than 0°C, more preferably of less than -10°C, as measured as measured according to ASTM D-3418.
- said (per)fluoro-elastomer comprises recurring units derived from the (per)fluorinated monomers cited above.
- CF 3 , C 2 F 5 , C 3 F 7 ; - fluorosilanes, such as CF 3 -C 2 H 4 -Si(R f3 ) 3 wherein each of R f3 is independently selected from Cl, C 1 -C 3 alkyl or C 1 -C 3 alkoxy, and CH 2 CH 2 -Si(R f4 ) 3 wherein each of R f4 is selected from H, F and C 1 -C 3 alkyl.
- said (per)fluoroelastomer further comprises recurring units derived from at least one bis-olefin.
- the resulting (per)fluoroelastomer typically comprises from 0.01% to 5% by moles of units deriving from the bis-olefin with respect to the total amount of units in the polymer.
- said (per)fluoroelastomer may comprise cure sites, either as pendant groups bonded to certain recurring units or as ends groups of the polymer chain, said cure sites comprising at least one iodine or bromine atom, more preferably at least one iodine atom.
- cure-site containing monomers of type CSM2-A and CSM2-B suitable to the purposes of the present invention are notably those described in patents US 4281092 DU PONT , US 5447993 DU PONT and US 5789489 DU PONT .
- said (per)fluoroelastomer comprises iodine or bromine cure sites in an amount of 0.001 to 10% wt.
- iodine cure sites are those selected for maximizing curing rate, so that (per)fluoroelastomers comprising iodine cure-sites are preferred.
- the content of iodine and/or bromine in the (per)fluoroelastomer should be of at least 0.05 % wt, preferably of at least 0.1 % weight, more preferably of at least 0.15 % weight, with respect to the total weight of the (per)fluoroelastomer.
- amounts of iodine and/or bromine not exceeding preferably 7 % wt, more specifically not exceeding 5 % wt, or even not exceeding 4 % wt, with respect to the total weight of the (per)fluoroelastomer are those generally selected for avoiding side reactions and/or detrimental effects on thermal stability.
- iodine or bromine cure sites of these preferred embodiments of the invention might be comprised as pending groups bound to the backbone of the (per)fluoroelastomer polymer chain (by means of incorporation in the (per)fluoroelastomer chain of recurring units derived from monomers of (CSM-1) type, as above described, and preferably of monomers of (CSM-1A) to (CSM1-D), as above detailed) or might be comprised as terminal groups of said polymer chain.
- the iodine and/or bromine cure sites are comprised as pending groups bound to the backbone of the (per)fluoroelastomer polymer chain.
- the (per)fluoroelastomer according to this embodiment generally comprises recurring units derived from iodine or bromine containing monomers (CSM-1) in amounts of 0.05 to 5 mol per 100 mol of all other recurring units of the (per)fluoroelastomer, so as to advantageously ensure above mentioned iodine and/or bromine weight content.
- the iodine and/or bromine cure sites are comprised as terminal groups of the (per)fluoroelastomer polymer chain;
- the fluoroelastomer according to this embodiment is generally obtained by addition to the polymerization medium during fluoroelastomer manufacture of anyone of: - iodinated and/or brominated chain-transfer agent(s);
- suitable chain-chain transfer agents are typically those of formula R f (I) x (Br) y , in which R f is a (per)fluoroalkyl or a (per)fluorochloroalkyl containing from 1 to 8 carbon atoms, while x and y are integers between 0 and 2, with 1 ⁇ x+y ⁇ 2 (see, for example, patents US 4243770 DAIKIN IND LTD and US 4943622 NIPPON MEKTRON KK ; and - alkali metal or alkaline-earth metal iodides and/or brom
- fluoroelastomers having the following compositions (in mol %): (i) vinylidene fluoride (VDF) 35-85 %, hexafluoropropene (HFP) 10-45 %, tetrafluoroethylene (TFE) 0-30 %, perfluoroalkyl vinyl ethers (PAVE) 0-15 %, bis-olefin (OF) 0-5 %; (ii) vinylidene fluoride (VDF) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 5 ⁇ 50 %, tetrafluoroethylene (TFE) 0-20 %, bis-olefin (OF) 0-5 %; (iii) vinylidene fluoride (VDF) 20-30 %, C 2 -C 8 non-fluorin
- Suitable examples of (per)fluoroelastomers are the products sold by SOLVAY SPECIALTY POLYMERS S.p.A. under the trade name Tecnoflon ® , such as for example Tecnoflon ® PL 855.
- said silicone elastomer has a T g of less than -10°C, more preferably of less than -30°C, and even more preferably of less than -50°C as measured as measured according to ASTM D-3418.
- said silicone elastomer comprises recurring units derived from silicon-containing monomers, and optionally further hydrogenated monomers and/or (per)fluorinated monomers as disclosed above.
- silicon-containing monomer it is hereby intended to denote a linear or branched monomer containing alternating silicon and oxygen atoms.
- said silicone elastomer is a polyorganosiloxane-based silicone rubber base, such as a polydimethyl siloxane containing crosslinking groups having hydroxyl, vinyl or hexenyl groups, or a polymethylphenyl siloxane.
- silicone elastomers are the products sold by Dow Corning Corp. (U.S.A.) under the trade name Silastic, such as Silastic 35U and Silastic TR-55 (dimethyl vinyl terminated, dimethyl organosiloxane).
- Said groups (N) are not particularly limited, provided that it contains at least one nitrogen atom.
- examples said of groups (N) are amino, amide, imino, nitrile, urethane and urea groups.
- the thickness of said layer (L1) is not particularly limited.
- said layer (L1) has a thickness of from 1 nm to 10 ⁇ m.
- said layer (L1) is a continuous layer, completely covering said surface (S).
- said layer (L1) can be a discontinuous layer, partially covering said surface (S), i.e. said surface (S) comprises at least one area that is not covered by said layer (L1).
- said compound (M) comprises at least one metal selected from the group consisting of: Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, Ga and alloys thereof.
- said compound (M) comprises at least one metal selected from the group consisting of Ni, Cu, Pd, Co, Ag, Au, Pt, Sn and alloys thereof. Even more preferably, said compound (M) comprises Cu and Pd.
- said elastomeric composition (C) typically comprises at least one elastomer, for example in the form of slabs, powder, crumbs, liquids, gels; and further ingredients.
- Suitable further ingredients and their amounts can be selected by the skilled person, depending on the type of elastomer used, the conditions used in the cross-linking step and/or the properties desired in the final article.
- - curing agents such as polyhydroxylic compounds (for example Bisphenol A), triallyl-isocyanurate (TAIC) and organic peroxide (for example di-tertbutyl peroxide, 2,4-dichloro benzoyl peroxide, dibenzoyl peroxide, bis(1,1-diethylpropyl)peroxide, bis(1- ethyl-1-methylpropyl)peroxide, 1,1-diethylpropyl-1-ethyl-1-methylpropyl- peroxide, 2,5-dimethyl-2,5-bis(tert-amylperoxy)hexane, dicumyl peroxide, di-tert-butyl perbenzoate, bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate and 2,5-bis(tert-butylper- oxy)-2,5-dimethylhexane, which is
- said curing agents are in an amount of from 0.5 to 15 phr (i.e., parts by weight per 100 parts by weight of the elastomer), more preferably of from 2 to 10 phr.
- composition (C) said metal compounds are in an amount of from 0.5 to 15 phr, more preferably of from 1 to 10 phr.
- composition (C) said conventional additives are in an amount of from 0.5 to 50 phr, more preferably of from 3 to 40 phr.
- the composition (C) can further comprise an organosilane coupling agent, preferably in an amount of from 0.1 wt.% to 1.5 wt.% of said composition (C).
- Said composition (C) is typically manufactured by using standard methods.
- Mixer devices such as internal mixers or open mill mixers can be used.
- step (i) of the process of the present invention said article is obtained by curing said composition (C).
- composition (C) can be selected by the skilled person depending on the elastomer and the curing agent used.
- curing can be performed at a temperature of from 100°C to 250°C, preferably from 150°C to 200°C, for a time of from 5 to 30 minutes.
- curing can be performed at a temperature of from 100°C to 200°C, for a time of from 5 to 15 minutes.
- said step (ii) is performed by treating said surface (S-1) in the presence of a nitrogen-containing gas.
- said nitrogen-containing gas is preferably selected from N 2 , NH 3 or mixtures thereof, optionally in admixture with nitrogen-free gas such as CO 2 and/or H 2 . More preferably, said nitrogen-containing gas is a mixture of N 2 and H 2 .
- the gas rate can be selected by the skilled person. Good results have been obtained by using gas flow between 5 nl/min and 15 nl/min, preferably of about 10 nl/min.
- said step (ii) is performed by an atmospheric plasma process.
- said atmospheric plasma process is performed under atmospheric pressure and with an equivalent corona dose of from 50 Wmin/m 2 to 30,000 Wmin/m 2 , more preferably of from 500 Wmin/m 2 to 15000 Wmin/m 2 .
- said at least one surface (S-1) is continuously treated by said atmospheric plasma process in the presence of a nitrogen-containing gas, so as to provide a nitrogen-containing surface (S-2).
- the Applicant has found that the so-treated surface (S-2) provides outstanding adhesion with a layer (L1) comprising at least one metal compound, applied thereto as disclosed below.
- said composition (C1) is in a solution or a colloidal suspension of the metallization catalyst in a suitable solvent, such as water.
- step (iii) is performed by dipping the elastomer as obtained in step (ii) in said composition (C1).
- compounds that may be employed as metallization catalysts in the method of the present invention are selected in the group comprising Pd, Pt, Rh, Ir, Ni, Cu, Ag and Au catalysts.
- the metallization catalyst is selected from Pd catalysts, such as PdCl 2 .
- said composition (C2) is an electroless metallization plating bath, comprising at least one compound (M1), at least one reducing agent, at least one liquid medium and, optionally, one or more additives.
- said compound (M1) comprises one or more metal salts. More preferably, said compound (M1) preferably comprises one or more metal salts of the metals listed above with respect to compound (M).
- said reducing agent is selected from the group comprising formaldehyde, sodium hypophosphite, hydrazine, glycolic acid and glyoxylic acid.
- said liquid medium is selected from the group comprising water, organic solvents and ionic liquids.
- alcohols are preferred such as ethanol.
- Non-limitative examples of suitable ionic liquids include, notably, those comprising as cation a sulfonium ion or an imidazolium, pyridinium, pyrrolidinium or piperidinium ring, said ring being optionally substituted on the nitrogen atom, in particular by one or more alkyl groups with 1 to 8 carbon atoms, and on the carbon atoms, in particular by one or more alkyl groups with 1 to 30 carbon atoms.
- the ionic liquid is advantageously selected from those comprising as anion those chosen from halides anions, perfluorinated anions and borates.
- additives are selected from the group comprising salts, buffers and other materials suitable for enhancing stability of the catalyst in the liquid composition.
- said step (iv) is performed at a temperature above 30°C, for example between 40°C and 50°C.
- said step (iv) is performed so as to provide a continuous layer (L1), which completely covers said surface (S), for example by dipping the elastomer as obtained in step (iii) in said composition (C2).
- said step (iv) may be performed so as to provide a discontinuous layer (L1), which partially covers said surface (S).
- steps (iii) and (iv) are performed as a single step [step (iii-D)], more preferably by electroless deposition.
- electroless deposition it is meant a redox process typically carried out in a plating bath between a metal cation and a proper chemical reducing agent suitable for reducing said metal cation in its elemental state.
- step (iii) and step (iv) apply whether steps (iii) and (iv) are performed separately or when step (iii) and step (iv) are performed as a single step (iii-D).
- said composition (C3) is an electrolytic solution, comprising at least one compound (M2), at least one metal halide and, optionally, at least one ionic liquid as defined above.
- Said compound (M2) can be the same or different from said compound (M1).
- said compound (M2) is a metal salt deriving from Al, Ni, Cu, Ag, Au, Cr, Co, Sn, Ir, Pt and alloys thereof.
- said metal halide is PdCl 2 .
- said step (v) is performed by electro-deposition.
- electro-deposition it is meant a process using electrical current to reduce metal cations from an electrolytic solution.
- Table 1 Ingredients Amount (phr) Tecnoflon ® PL855 100 Carbon Black N990 30 ZnO 5 Luperox ® 101XL45 3 TAIC 4
- composition thus obtained was press-cured for 10 minutes at 170°C, so as to form plaques of 2 mm thick and 130 mm of side.
- the plaques were then post-cured in an oven (in air) for 24 hours at 250°C.
- the plaques thus obtained were then cleaned with a lab cloth soaked with isopropyl alcohol (IPA), in order to remove dirt and contaminants.
- IPA isopropyl alcohol
- Plaque 1C One of the plaque thus obtained was used as reference plaque (hereinafter referred to as “ Plaque 1C ").
- DBD Dielectric Barrier Discharge
- the treatment resulted in an equivalent corona dose of about 8700 W min/m 2 .
- Plaque AP The plaque thus obtained will be hereinafter referred to as “ Plaque AP ”.
- Plaque AP obtained according to the procedure disclosed in step (a) was subjected to electroless deposition in order to obtain a layer of metallic copper.
- the plaque was cleaned by dipping in a suitable solution containing isopropyl alcohol and, then, contacted with a PdCl 2 solution.
- the palladium ions were reduced to metallic palladium. Then, electroless deposition of copper was performed by dipping the sample in the bath containing the Atotech’s Printogant PV solution, for 90 seconds, at 45°C, so as the metallic copper was deposited on the surface of the plaque.
- Plaque 2 The plaque thus obtained will be hereinafter referred to as “ Plaque 2 ”.
- Plaque 3C The plaque thus obtained will be hereinafter referred to as “ Plaque 3C ”.
- One plaque obtained according to the procedure described in Example 1 above was deposited with a copper layer by sputtering technique, i.e. in particular by eroding copper atoms from a copper electrode using an argon plasma and depositing said copper onto the plaque.
- Plaque 4C The plaque thus obtained will be hereinafter referred to as “ Plaque 4C ”.
- Attenuated total reflection is a sampling technique used in conjunction with infrared (IR) spectroscopy which enables samples to be examined directly in the solid or liquid state.
- FTIR Fourier transform infrared
- a piece measuring 20mm x 30mm of the treated plaque was subjected to measurements performed with Ge crystal, with a resolution of 2cm -1 and 256 scans.
- the results were compared by performing spectral subtraction between the spectra obtained for Plaque AP and Plaque 1C, and weak positive bands were observed in the region at about 3300 cm -1 and from 1680 cm -1 to 1500 cm -1 , which were compatible with the presence of chemical groups containing nitrogen atoms like amide, urethanes and ureas.
- X-ray Photoelectron Spectroscopy is a surface analysis, which provides quantitative and chemical state information from the surface of the material being studied.
- the average depth of analysis was approximately 5 nm, so that it was possible to obtain the actual composition of the sample surface.
- Plaque 2 which is an examples of the multilayer article according to the present invention, contains the nitrogen-containing groups, as well as palladium and copper atoms.
- the adhesion of the metallic layer was evaluated on the following plaques: - Plaque 2 obtained according to the procedure described in Example 2, - Plaque 3C obtained according to the procedure described in Comparative Example 3 and - Plaque 4C obtained according to the procedure described in Comparative Example 4.
- the adhesion was evaluated as follows: using a cutting tool, two series of perpendicular cuts were performed on the metallic layer of Plaque 2, Plaque 3C and Plaque 4C, in order to create a lattice pattern on them. A piece of tape was then applied and smoothened over the lattice and removed with an angle of 180° with respect to the metallic layer.
- the adhesion of metallic layer was then assessed for Plaque 2, Plaque 3C and Plaque 4C by comparing the lattice of cuts with the ASTM D3359 standard procedure.
- the classification of test results ranged from 5B to 0B, whose descriptions are depicted in Table 4 herein below.
- Table 4 ASTM D3359 Classification Description 5B The edges of the cuts are completely smooth; none of the squares of the lattice is detached. 4B Detachment of flakes of the coating at the intersections of the cuts. A cross cut area not significantly greater than 5% is affected. 3B The coating has flaked along the edges and/or at the intersection of the cuts. A cross cut area significantly greater than 5%, but not significantly greater than 15% is affected.
- the coating has flaked along the edges of the cuts partly or wholly in large ribbons, and/or it has flaked partly of wholly on different parts of the squares.
- the coating has flaked along the edges of the cuts in large ribbons and/or some squares have detached partly or wholly.
- Plaque 2 obtained according to the procedure described in Example 2 and Plaque 1C obtained according to the procedure described in Example 1 were evaluated with tensile tests following the DIN 53504 S2 standard procedure.
Abstract
Description
- This application claims priority from European application No. 14193990.0, filed on 20th November 2014, the whole content of this application being incorporated herein by reference for all purposes.
- The present invention relates to a multi-layered elastomer article and to a method for its manufacturing.
- (Per)fluoroelastomers are known to be relatively chemically inert, thermally stable polymers, owing primarily to the strength of the carbon-fluorine bonds present in the molecule.
- Because of their properties, the (per)fluoroelastomers are desirable in many applications which require elastomeric materials able to provide high performances, such as withstanding to high temperatures.
- However, a great number of applications in the field of oil and gas, electronics, automotive, and aerospace require the (per)fluoroelastomers, for example, to have electrical and thermal conductivity or to provide a barrier to gases and liquids.
- With the aim to provide (per)fluoroelastomers having the above properties, it has been proposed in the art to adhesively bond metals to (per)fluoroelastomers.
- Conventional approaches, such as for example vapour coating, sputtering or ion bombardment processes, comprise chemically or physically roughen the metal surface, followed by a thermal fusion or adhering with the intermediary of an adhesive layer (also called primer) between the outmost fluoropolymer layer and the metal, which also has to possess outstanding adhesion properties towards additional top-coat (outer) layers made from fluoropolymers.
- For example,
WO WO 2013/101822 3M INNOVATIVE PROPERTIES CO. - However, high performing polymers – including, in particular, (per)fluoroelastomers and silicone rubbers – have low surface energy, and consequently poor adhesion with respect to metal materials.
- Thus, the high performing polymers coated with metal layers using conventional approaches can suffer of problems such as easy peeling of the metallic coating from the substrate and poor durability of the coating.
- In the field of semi-crystalline polymers,
WO WO 2014/154733 SOLVAY SPECIALTY POLYMERS S.P.A. - However, semi-crystalline polymers, such as ECTFE, and elastomers have different chemical-physical properties and are used in different applications. Also, semi-crystalline polymers do not undergo to elongation and, hence, they are not affected by the problems typically encountered when using elastomers.
- In particular, defects in the metallic layer applied on the surface of the elastomer can become particularly evident when the elastomer undergoes to elongation, resulting in a loss of continuity in the metal layer and consequent decrease or loss of the properties imparted by the metal coating, such as for example barrier to fluids and thermal/electrical conductivity.
-
FR 2139998 DR. ING. MAX SCHLOTTER -
US 2009/0017319 A FRAMATOME CONNECTORS INT. - The Applicant faced the problem to provide an elastomer article having high adhesion to a metallic layer, such that defects in the metallic layer are avoided or at least minimized even after the elastomer has undergone to elongation.
- Thus, in a first aspect, the present invention relates to a multi-layered article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S)] comprising:
- nitrogen-containing groups [groups (N)] and
- at least one layer [layer (L1)] adhered to said surface (S) comprising at least one metal compound [compound (M)]. - In a preferred embodiment, said groups (N) are grafted onto said surface (S).
- Without being bounded by any theory, the Applicant believes that at least part of said groups (N) grafted onto said surface (S) form chemical bonds with said at least one compound (M), thus obtaining an outstanding adhesion between said surface (S) comprising groups (N) and said layer (L1) comprising compound (M).
- The expression “chemical bonds” is intended to indicate any type of chemical bond, such as for example covalent bond, ionic bond, dipolar (or coordinate) bond, between at least part of groups (N) grafted on the surface of the elastomer and compound (M).
- Advantageously, the article according to the present invention comprising said layer (L1) adhered to said surface (S) provides electrical and thermal conductivity and a barrier to gases and liquids, and can withstand extreme environmental conditions due to chemical resistance, abrasion resistance and wear resistance, while maintaining its typical flexibility and mechanical properties.
- Then, in a second aspect, the present invention relates to a method for manufacturing a multi-layered article, said method comprising the steps of:
(i) providing an article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S-1)];
(ii) forming nitrogen-containing groups [groups (N)] on said at least one surface (S-1) so as to provide an elastomer article having at least one nitrogen-containing surface [surface (S-2)];
(iii) contacting said at least one surface (S-2) with a first composition [composition (C1)] comprising at least one metallization catalyst, so as to provide an article having at least one surface [surface (S-3)] containing groups (N) and at least one metallization catalyst; and
(iv) contacting said at least one surface (S-3) with a second composition [composition (C2)] containing at least one metal compound [compound (M1)], so as to provide a multi-layered article having at least one surface [surface (S)] comprising groups (N) and at least one layer (L1) adhered to said surface (S) comprising at least one metal compound (M). - Optionally, the above method comprises after step (iv), step (v) of applying a third composition [composition (C3)] containing at least one metal compound [compound (M2)] onto said surface (S).
- Preferably, said multi-layered article is in the form of a film or a shaped article.
- The thickness of said film is not particularly limited. For example, said film can have a thickness of between 0.5 mm and 10 mm.
- The term "elastomer” as used within the present description and in the following claims indicates amorphous polymers or polymers having a low degree of crystallinity (crystalline phase less than 20% by volume) and a glass transition temperature value (Tg), measured according to ASTM D3418, below room temperature. More preferably, the elastomer according to the present invention has a Tg below 5°C, even more preferably below 0°C.
- Preferably, said elastomer comprises recurring units derived from at least one at least one (per)fluorinated monomer and/or at least one hydrogenated monomer. In a preferred embodiment, said monomers are free of nitrogen atoms.
- By the expression “at least one (per)fluorinated monomer, it is hereby intended to denote a polymer comprising recurring units derived from one or more than one (per)fluorinated monomers. In the rest of the text, the expression “(per)fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that it denote both one or more than one fluorinated monomers as defined above. The prefix "(per)" in the expression "(per)fluorinated monomer” and in the term “(per)fluoroelastomer” means that the monomer or the elastomer can be fully or partially fluorinated.
- Non limitative examples of suitable (per)fluorinated monomers include, notably, the followings:
- C3-C8 perfluoroolefins, such as tetrafluoroethylene (TFE) and hexafluoropropene (HFP);
- C2-C8 hydrogenated fluoroolefins, such as vinylidene fluoride (VDF), vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene (TrFE);
- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins, such as chlorotrifluoroethylene (CTFE);
- CH2=CH-Rf0 wherein Rf0 is a C1-C6 (per)fluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups;
- CH2=CFORf1, wherein Rf1 is a C1-C6 fluoro- or perfluoroalkyl group, such as CF3, C2F5, C3F7;
- CF2=CFORf2, wherein Rf2 is a C1-C6 fluoro- or perfluoroalkyl group, such as CF3, C2F5, C3F7; or a C1-C12 oxyalkyl or a C1-C12 (per)fluorooxyalkyl group comprising one or more ether groups, such as perfluoro-2-propoxy-propyl; or a group of formula -CF2ORf3 in which Rf3 is a C1-C6 fluoro- or perfluoroalkyl or a C1-C6 (per)fluorooxyalkyl group comprising one or more ether groups, such as -C2F5-O-CF3;
- CF2=CFORf4, wherein Rf4 is a C1-C12 alkyl or (per)fluoroalkyl group; a C1-C12 oxyalkyl; or a C1-C12 (per)fluorooxyalkyl; said Rf4 comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
- fluorodioxoles, such as perfluorodioxoles;
- fluorosilanes, such as CF3-C2H4-Si(Rf5)3 or Ar-Si(Rf5)3 wherein each of Rf5 is independently selected from Cl, C1-C3 alkyl or C1-C3 alkoxy, and Ar is a phenyl ring optionally substituted with a C1-C6 fluoro- or perfluoroalkyl group, e.g. CF3, C2F5, C3F7 or a C1-C6 (per)fluorooxyalkyl group comprising one or more ether groups, such as -C2F5-O-CF3; and CH2=CH2-Si(Rf6)3 wherein each of Rf6 is independently selected from H, F and C1-C3 alkyl, provided that at least one of said Rf6 is F. - The expressions “at least one hydrogenated monomer” is intended to mean that the polymer may comprise recurring units derived from one or more than one hydrogenated monomers.
- By the expression “hydrogenated monomer”, it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
- Non limitative examples of suitable hydrogenated monomers include, notably, non-fluorinated monomers such as C2-C8 non-fluorinated olefins (OI), in particular C2-C8 non-fluorinated alpha-olefins (OI), including ethylene, propylene, 1-butene; diene monomers; vinyl monomers such as vinyl acetate and methyl-vinyl ether (MVE); acrylic monomers, like methyl methacrylate, butyl acrylate; styrene monomers, like styrene and p‑methylstyrene; and silicon-containing monomers.
- According to a preferred embodiment, said elastomer is a (per)fluoro-elastomer or a silicone elastomer.
- Preferably, said (per)fluoro-elastomer has a Tg of less than 0°C, more preferably of less than -10°C, as measured as measured according to ASTM D-3418.
- Typically, said (per)fluoro-elastomer comprises recurring units derived from the (per)fluorinated monomers cited above.
- More preferably, said (per)fluoro-elastomer comprises recurring units derived from:
- C3-C8 perfluoroolefins, such as tetrafluoroethylene (TFE) and hexafluoropropene (HFP);
- C2-C8 hydrogenated fluoroolefins, such as vinylidene fluoride (VDF), vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene (TrFE);
- CF2=CFORf1, wherein Rf1 is a C1-C6 fluoro- or perfluoroalkyl group, such as CF3, C2F5, C3F7, or a group of formula -CFOCF2ORf2 wherein Rf2 is a C1-C6 fluoro- or perfluoroalkyl group, e.g. CF3, C2F5, C3F7;
- fluorosilanes, such as CF3-C2H4-Si(Rf3)3 wherein each of Rf3 is independently selected from Cl, C1-C3 alkyl or C1-C3 alkoxy, and CH2=CH2-Si(Rf4)3 wherein each of Rf4 is selected from H, F and C1-C3 alkyl. - Optionally, said (per)fluoroelastomer further comprises recurring units derived from at least one bis-olefin.
- Non limiting examples of suitable bis-olefins are selected from those of formulae below:
- R1R2C=CH-(CF2)j-CH=CR3R4 wherein j is an integer between 2 and 10, preferably between 4 and 8, and R1, R2, R3, R4, equal or different from each other, are -H, -F or C1-C5 alkyl or (per)fluoroalkyl group;
- A2C=CB-O-E-O-CB=CA2 ,wherein each of A, equal or different from each other, is independently selected from -F, -Cl, and -H; each of B, equal or different from each other is independently selected from -F, -Cl, -H and -ORB, wherein RB is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; E is a divalent group having 2 to 10 carbon atoms, optionally fluorinated, which may be inserted with ether linkages; preferably E is a -(CF2)z- group, with z being an integer from 3 to 5; and
- R6R7C=CR5-E-O-CB=CA2, wherein E, A and B have the same meaning as above defined; R5, R6, R7, equal or different from each other, are -H, -F or C1-C5 alkyl or fluoroalkyl group. - When a bis-olefin is employed, the resulting (per)fluoroelastomer typically comprises from 0.01% to 5% by moles of units deriving from the bis-olefin with respect to the total amount of units in the polymer.
- Optionally, said (per)fluoroelastomer may comprise cure sites, either as pendant groups bonded to certain recurring units or as ends groups of the polymer chain, said cure sites comprising at least one iodine or bromine atom, more preferably at least one iodine atom.
- Among cure-site containing recurring units, mention can be notably made of:
(CSM-1) iodine or bromine containing monomers of formula:
wherein each of AHf, equal to or different from each other and at each occurrence, is independently selected from F, Cl, and H; BHf is any of F, Cl, H and ORHf B, wherein RHf B is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; each of WHf equal to or different from each other and at each occurrence, is independently a covalent bond or an oxygen atom; EHf is a divalent group having 2 to 10 carbon atom, optionally fluorinated; RHf is a branched or straight chain alkyl radical, which can be partially, substantially or completely fluorinated; and RHf is a halogen atom selected from the group consisting of Iodine and Bromine; which may be inserted with ether linkages; preferably E is a –(CF2)m- group, with m being an integer from 3 to 5;
(CSM-2) ethylenically unsaturated compounds comprising cyanide groups, possibly fluorinated. - Among cure-site containing monomers of type (CSM1), preferred monomers are those selected from the group consisting of:
(CSM1-A) iodine-containing perfluorovinylethers of formula:
with m being an integer from 0 to 5 and n being an integer from 0 to 3, with the provisio that at least one of m and n is different from 0, and Rfi being F or CF3; (as notably described in patentsUS 4745165 AUSIMONT SPA US 4564662 MINNESOTA MINING EP 199138 DAIKIN IND LTD
(CSM-1B) iodine-containing ethylenically unsaturated compounds of formula:
CX1X2=CX3-(CF2CF2)p-I
wherein each of X1, X2 and X3, equal to or different from each other, are independently H or F; and p is an integer from 1 to 5; among these compounds, mention can be made of CH2=CHCF2CF2I, I(CF2CF2)2CH=CH2, ICF2CF2CF=CH2, I(CF2CF2)2CF=CH2;
(CSM-1C) iodine-containing ethylenically unsaturated compounds of formula:
CHR=CH-Z-CH2CHR-I
wherein R is H or CH3, Z is a C1-C18 (per)fluoroalkylene radical, linear or branched, optionally containing one or more ether oxygen atoms, or a (per)fluoropolyoxyalkylene radical; among these compounds, mention can be made of CH2=CH-(CF2)4CH2CH2I, CH2=CH-(CF2)6CH2CH2I, CH2=CH-(CF2)8CH2CH2I, CH2=CH-(CF2)2CH2CH2I;
(CSM-1D) bromo and/or iodo alpha-olefins containing from 2 to 10 carbon atoms such as bromotrifluoroethylene or bromotetrafluorobutene described, for example, inUS 4035565 DU PONT US 4694045 DU PONT - Among cure-site containing monomers of type (CSM2), preferred monomers are those selected from the group consisting of:
(CSM2-A) perfluorovinyl ethers containing cyanide groups of formula CF2=CF-(OCF2CFXCN)m-O-(CF2)n-CN, with XCN being F or CF3, m being 0, 1, 2, 3 or 4; n being an integer from 1 to 12;
(CSM2-B) perfluorovinyl ethers containing cyanide groups of formula CF2=CF-(OCF2CFXCN)m’-O-CF2—CF(CF3)-CN, with XCN being F or CF3, m’ being 0, 1, 2, 3 or 4.
Specific examples of cure-site containing monomers of type CSM2-A and CSM2-B suitable to the purposes of the present invention are notably those described in patentsUS 4281092 DU PONT US 5447993 DU PONT US 5789489 DU PONT - Preferably, said (per)fluoroelastomer comprises iodine or bromine cure sites in an amount of 0.001 to 10% wt. Among these, iodine cure sites are those selected for maximizing curing rate, so that (per)fluoroelastomers comprising iodine cure-sites are preferred.
- According to this embodiment, for ensuring acceptable reactivity it is generally understood that the content of iodine and/or bromine in the (per)fluoroelastomer should be of at least 0.05 % wt, preferably of at least 0.1 % weight, more preferably of at least 0.15 % weight, with respect to the total weight of the (per)fluoroelastomer.
- On the other side, amounts of iodine and/or bromine not exceeding preferably 7 % wt, more specifically not exceeding 5 % wt, or even not exceeding 4 % wt, with respect to the total weight of the (per)fluoroelastomer, are those generally selected for avoiding side reactions and/or detrimental effects on thermal stability.
- These iodine or bromine cure sites of these preferred embodiments of the invention might be comprised as pending groups bound to the backbone of the (per)fluoroelastomer polymer chain (by means of incorporation in the (per)fluoroelastomer chain of recurring units derived from monomers of (CSM-1) type, as above described, and preferably of monomers of (CSM-1A) to (CSM1-D), as above detailed) or might be comprised as terminal groups of said polymer chain.
- According to a first embodiment, the iodine and/or bromine cure sites are comprised as pending groups bound to the backbone of the (per)fluoroelastomer polymer chain. The (per)fluoroelastomer according to this embodiment generally comprises recurring units derived from iodine or bromine containing monomers (CSM-1) in amounts of 0.05 to 5 mol per 100 mol of all other recurring units of the (per)fluoroelastomer, so as to advantageously ensure above mentioned iodine and/or bromine weight content.
- According to a second preferred embodiment, the iodine and/or bromine cure sites are comprised as terminal groups of the (per)fluoroelastomer polymer chain; the fluoroelastomer according to this embodiment is generally obtained by addition to the polymerization medium during fluoroelastomer manufacture of anyone of:
- iodinated and/or brominated chain-transfer agent(s); suitable chain-chain transfer agents are typically those of formula Rf(I)x(Br)y, in which Rf is a (per)fluoroalkyl or a (per)fluorochloroalkyl containing from 1 to 8 carbon atoms, while x and y are integers between 0 and 2, with 1 ≤ x+y ≤ 2 (see, for example, patentsUS 4243770 DAIKIN IND LTD US 4943622 NIPPON MEKTRON KK
- alkali metal or alkaline-earth metal iodides and/or bromides, such as described notably in patentUS 5173553 AUSIMONT SRL - Among specific compositions of said (per)fluoroelastomer, which are suitable for the purpose of the present invention, mention can be made of fluoroelastomers having the following compositions (in mol %):
(i) vinylidene fluoride (VDF) 35-85 %, hexafluoropropene (HFP) 10-45 %, tetrafluoroethylene (TFE) 0-30 %, perfluoroalkyl vinyl ethers (PAVE) 0-15 %, bis-olefin (OF) 0-5 %;
(ii) vinylidene fluoride (VDF) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 5‑50 %, tetrafluoroethylene (TFE) 0-20 %, bis-olefin (OF) 0-5 %;
(iii) vinylidene fluoride (VDF) 20-30 %, C2-C8 non-fluorinated olefins (Ol) 10‑30 %, hexafluoropropene (HFP) and/or perfluoroalkyl vinyl ethers (PAVE) 18-27 %, tetrafluoroethylene (TFE) 10-30 %, bis-olefin (OF) 0-5 %;
(iv) tetrafluoroethylene (TFE) 50-80 %, perfluoroalkyl vinyl ethers (PAVE) 20‑50 %, bis-olefin (OF) 0-5 %;
(v) tetrafluoroethylene (TFE) 45-65 %, C2-C8 non-fluorinated olefins (Ol) 20‑55 %, vinylidene fluoride 0-30 %, bis-olefin (OF) 0-5 %;
(vi) tetrafluoroethylene (TFE) 32-60 % mol %, C2-C8 non-fluorinated olefins (Ol) 10-40 %, perfluoroalkyl vinyl ethers (PAVE) 20-40 %, fluorovinyl ethers (MOVE) 0-30 %, bis-olefin (OF) 0-5 %;
(vii) tetrafluoroethylene (TFE) 33-75 %, perfluoroalkyl vinyl ethers (PAVE) 15‑45 %, vinylidene fluoride (VDF) 5-30 %, hexafluoropropene HFP 0-30 %, bis-olefin (OF) 0-5 %;
(viii) vinylidene fluoride (VDF) 35-85 %, fluorovinyl ethers (MOVE) 5-40 %, perfluoroalkyl vinyl ethers (PAVE) 0-30 %, tetrafluoroethylene (TFE) 0-40 %, hexafluoropropene (HFP) 0-30 %, bis-olefin (OF) 0-5 %;
(ix) tetrafluoroethylene (TFE) 20-70 %, fluorovinyl ethers (MOVE) 30-80 %, perfluoroalkyl vinyl ethers (PAVE) 0-50 %, bis-olefin (OF) 0-5 %. - Suitable examples of (per)fluoroelastomers are the products sold by SOLVAY SPECIALTY POLYMERS S.p.A. under the trade name Tecnoflon®, such as for example Tecnoflon® PL 855.
- Preferably, said silicone elastomer has a Tg of less than -10°C, more preferably of less than -30°C, and even more preferably of less than -50°C as measured as measured according to ASTM D-3418.
- Typically, said silicone elastomer comprises recurring units derived from silicon-containing monomers, and optionally further hydrogenated monomers and/or (per)fluorinated monomers as disclosed above.
- By the expression “silicon-containing monomer”, it is hereby intended to denote a linear or branched monomer containing alternating silicon and oxygen atoms.
- Non limitative examples of suitable silicon-containing monomers include:
- silane, such as CH2=CH2-Si(Rf7)3 wherein each of Rf7 is independently selected from H, F and C1-C3 alkyl;
- siloxane of formula (R)3Si-O-Si(R)3 and (R)2Si(OH)2, wherein each R is independently selected from H, linear or branched alkyl groups having from 1 to 6 carbon atoms, preferably methyl group, or phenyl group. - Typically, said silicone elastomer is a polyorganosiloxane-based silicone rubber base, such as a polydimethyl siloxane containing crosslinking groups having hydroxyl, vinyl or hexenyl groups, or a polymethylphenyl siloxane.
- Suitable examples of silicone elastomers are the products sold by Dow Corning Corp. (U.S.A.) under the trade name Silastic, such as Silastic 35U and Silastic TR-55 (dimethyl vinyl terminated, dimethyl organosiloxane).
- Said groups (N) are not particularly limited, provided that it contains at least one nitrogen atom. Examples said of groups (N) are amino, amide, imino, nitrile, urethane and urea groups.
- The thickness of said layer (L1) is not particularly limited. For example, said layer (L1) has a thickness of from 1 nm to 10 μm.
- Preferably, said layer (L1) is a continuous layer, completely covering said surface (S). However, depending on the application, said layer (L1) can be a discontinuous layer, partially covering said surface (S), i.e. said surface (S) comprises at least one area that is not covered by said layer (L1).
- Preferably, said compound (M) comprises at least one metal selected from the group consisting of: Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, Ga and alloys thereof.
- More preferably, said compound (M) comprises at least one metal selected from the group consisting of Ni, Cu, Pd, Co, Ag, Au, Pt, Sn and alloys thereof. Even more preferably, said compound (M) comprises Cu and Pd.
- Under step (i) of the process of the present invention, said elastomeric composition (C) typically comprises at least one elastomer, for example in the form of slabs, powder, crumbs, liquids, gels; and further ingredients.
- Suitable further ingredients and their amounts can be selected by the skilled person, depending on the type of elastomer used, the conditions used in the cross-linking step and/or the properties desired in the final article.
- Typically, further ingredients can be selected from the following:
- curing agents, such as polyhydroxylic compounds (for example Bisphenol A), triallyl-isocyanurate (TAIC) and organic peroxide (for example di-tertbutyl peroxide, 2,4-dichloro benzoyl peroxide, dibenzoyl peroxide, bis(1,1-diethylpropyl)peroxide, bis(1- ethyl-1-methylpropyl)peroxide, 1,1-diethylpropyl-1-ethyl-1-methylpropyl- peroxide, 2,5-dimethyl-2,5-bis(tert-amylperoxy)hexane, dicumyl peroxide, di-tert-butyl perbenzoate, bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate and 2,5-bis(tert-butylper- oxy)-2,5-dimethylhexane, which is sold under the trade name Luperox® 101XL45);
- metal compounds, in particular bivalent metal oxides and/or hydroxide, such as MgO, ZnO and Ca(OH)2; salts of a weak acid, such as Ba, Na, K, Pb, Ca stearate, benzoates, carbonates, oxalates, or phopshites; and mixtures thereof; and
- conventional additives, in particular fillers, such as carbon black and fumed silica; accelerators, such as ammonium, phosphonium and aminophosphonium salt; thickeners; pigments; antioxideant; stabilizers; processing aids. - Preferably, in composition (C), said curing agents are in an amount of from 0.5 to 15 phr (i.e., parts by weight per 100 parts by weight of the elastomer), more preferably of from 2 to 10 phr.
- Preferably, in composition (C), said metal compounds are in an amount of from 0.5 to 15 phr, more preferably of from 1 to 10 phr.
- Preferably, in composition (C), said conventional additives are in an amount of from 0.5 to 50 phr, more preferably of from 3 to 40 phr.
- Also, when the elastomer is a silicone elastomer, the composition (C) can further comprise an organosilane coupling agent, preferably in an amount of from 0.1 wt.% to 1.5 wt.% of said composition (C).
- Said composition (C) is typically manufactured by using standard methods.
- Typically, all the ingredients are first mixed together. Mixer devices such as internal mixers or open mill mixers can be used.
- Under step (i) of the process of the present invention, said article is obtained by curing said composition (C).
- The conditions for the curing of said composition (C) can be selected by the skilled person depending on the elastomer and the curing agent used.
- For example, when the elastomer is a fluoroelastomer, curing can be performed at a temperature of from 100°C to 250°C, preferably from 150°C to 200°C, for a time of from 5 to 30 minutes.
- Alternatively, when the elastomer is a silicone elastomer, curing can be performed at a temperature of from 100°C to 200°C, for a time of from 5 to 15 minutes.
- Preferably, in the method according to the present invention, said step (ii) is performed by treating said surface (S-1) in the presence of a nitrogen-containing gas.
- Under step (ii) of the present invention, said nitrogen-containing gas is preferably selected from N2, NH3 or mixtures thereof, optionally in admixture with nitrogen-free gas such as CO2 and/or H2. More preferably, said nitrogen-containing gas is a mixture of N2 and H2.
- The gas rate can be selected by the skilled person. Good results have been obtained by using gas flow between 5 nl/min and 15 nl/min, preferably of about 10 nl/min.
- Preferably, said step (ii) is performed by an atmospheric plasma process.
- Preferably, said atmospheric plasma process is performed under atmospheric pressure and with an equivalent corona dose of from 50 Wmin/m2 to 30,000 Wmin/m2, more preferably of from 500 Wmin/m2 to 15000 Wmin/m2.
- Advantageously, said at least one surface (S-1) is continuously treated by said atmospheric plasma process in the presence of a nitrogen-containing gas, so as to provide a nitrogen-containing surface (S-2).
- The Applicant has found that the so-treated surface (S-2) provides outstanding adhesion with a layer (L1) comprising at least one metal compound, applied thereto as disclosed below.
- Preferably, under step (iii) of the present invention, said composition (C1) is in a solution or a colloidal suspension of the metallization catalyst in a suitable solvent, such as water.
- Preferably, step (iii) is performed by dipping the elastomer as obtained in step (ii) in said composition (C1).
- Preferably, compounds that may be employed as metallization catalysts in the method of the present invention are selected in the group comprising Pd, Pt, Rh, Ir, Ni, Cu, Ag and Au catalysts.
- More preferably, the metallization catalyst is selected from Pd catalysts, such as PdCl2.
- Preferably, under step (iv), said composition (C2) is an electroless metallization plating bath, comprising at least one compound (M1), at least one reducing agent, at least one liquid medium and, optionally, one or more additives.
- Preferably, said compound (M1) comprises one or more metal salts. More preferably, said compound (M1) preferably comprises one or more metal salts of the metals listed above with respect to compound (M).
- Preferably, said reducing agent is selected from the group comprising formaldehyde, sodium hypophosphite, hydrazine, glycolic acid and glyoxylic acid.
- Preferably, said liquid medium is selected from the group comprising water, organic solvents and ionic liquids.
- Among organic solvents, alcohols are preferred such as ethanol.
- Non-limitative examples of suitable ionic liquids include, notably, those comprising as cation a sulfonium ion or an imidazolium, pyridinium, pyrrolidinium or piperidinium ring, said ring being optionally substituted on the nitrogen atom, in particular by one or more alkyl groups with 1 to 8 carbon atoms, and on the carbon atoms, in particular by one or more alkyl groups with 1 to 30 carbon atoms.
- Preferably, the ionic liquid is advantageously selected from those comprising as anion those chosen from halides anions, perfluorinated anions and borates.
- Preferably, additives are selected from the group comprising salts, buffers and other materials suitable for enhancing stability of the catalyst in the liquid composition.
- Preferably, said step (iv) is performed at a temperature above 30°C, for example between 40°C and 50°C.
- Preferably, said step (iv) is performed so as to provide a continuous layer (L1), which completely covers said surface (S), for example by dipping the elastomer as obtained in step (iii) in said composition (C2). However, depending on the application of the multi-layered article, said step (iv) may be performed so as to provide a discontinuous layer (L1), which partially covers said surface (S).
- Preferably, said steps (iii) and (iv) are performed as a single step [step (iii-D)], more preferably by electroless deposition.
- By “electroless deposition” it is meant a redox process typically carried out in a plating bath between a metal cation and a proper chemical reducing agent suitable for reducing said metal cation in its elemental state.
- The preferred conditions disclosed above with respect to step (iii) and step (iv) apply whether steps (iii) and (iv) are performed separately or when step (iii) and step (iv) are performed as a single step (iii-D).
- Preferably, said composition (C3) is an electrolytic solution, comprising at least one compound (M2), at least one metal halide and, optionally, at least one ionic liquid as defined above.
- Said compound (M2) can be the same or different from said compound (M1).
- Preferably, said compound (M2) is a metal salt deriving from Al, Ni, Cu, Ag, Au, Cr, Co, Sn, Ir, Pt and alloys thereof.
- Preferably, said metal halide is PdCl2.
- Preferably, said step (v) is performed by electro-deposition.
- Within the present description and in the following claims, by "electro-deposition" it is meant a process using electrical current to reduce metal cations from an electrolytic solution.
- Should the disclosure of any patents, patent applications and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
- The present invention will be now described in more detail with reference to the following examples, whose purpose if merely illustrative and not limitative of the scope of the invention.
- Materials
Tecnoflon® PL855 fluoroelastomer: TFE/PMVE/MOVE terpolymer having Mooney viscosity of about 54 and Tg of about -30°C, supplied by Solvay Specialty Polymers Italy S.p.A.
Luperox® 101XL45: 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, blend with calcium carbonate and silica, with 45 wt.% of solid content
TAIC: triallyl isocyanurate, with 75 wt.% of solid content
Commercial copper electroless solution Printoganth PV, supplied by Atotech
- Example 1 - Production of an elastomer article [Plaque 1C]
- The ingredients listed in the following Table 1 were mixed together in an open mill mixer.
Table 1 Ingredients Amount (phr) Tecnoflon® PL855 100 Carbon Black N990 30 ZnO 5 Luperox® 101XL45 3 TAIC 4 - The composition thus obtained was press-cured for 10 minutes at 170°C, so as to form plaques of 2 mm thick and 130 mm of side. The plaques were then post-cured in an oven (in air) for 24 hours at 250°C.
- The plaques thus obtained were then cleaned with a lab cloth soaked with isopropyl alcohol (IPA), in order to remove dirt and contaminants.
- One of the plaque thus obtained was used as reference plaque (hereinafter referred to as “Plaque 1C").
- Example 2 – Manufacture of a multi-layered elastomer article
- One of the plaques obtained according to the procedure described in Example 1 was treated as follows.
- Step (a) [Plaque AP]
- An atmospheric plasma treatment was performed on one surface of the plaque by means of a Dielectric Barrier Discharge (DBD) device with mobile upper electrode, in the following conditions:
electrode distance 3mm
gas flow 10 nl/min
gas composition 95% N2 + 5% H2
source power 400W
mobile electrode speed 2m/min and 3 passes - The treatment resulted in an equivalent corona dose of about 8700 W min/m2.
- The plaque thus obtained will be hereinafter referred to as “Plaque AP”.
- Step (b) [Plaque 2]
- Plaque AP obtained according to the procedure disclosed in step (a) was subjected to electroless deposition in order to obtain a layer of metallic copper.
- The plaque was cleaned by dipping in a suitable solution containing isopropyl alcohol and, then, contacted with a PdCl2 solution.
- The palladium ions were reduced to metallic palladium. Then, electroless deposition of copper was performed by dipping the sample in the bath containing the Atotech’s Printogant PV solution, for 90 seconds, at 45°C, so as the metallic copper was deposited on the surface of the plaque.
- The plaque thus obtained will be hereinafter referred to as “Plaque 2”.
- Comparative Example 3 – Manufacture of a comparative multi-layered elastomer article [Plaque 3C]
- One plaque obtained according to the procedure described in Example 1 above was treated according to the procedure described in Example 2, step (b), without performing the atmospheric plasma treatment.
- The plaque thus obtained will be hereinafter referred to as “Plaque 3C”.
- Comparative Example 4 – Manufacture of a comparative multi-layered elastomer article [Plaque 4C]
- One plaque obtained according to the procedure described in Example 1 above was deposited with a copper layer by sputtering technique, i.e. in particular by eroding copper atoms from a copper electrode using an argon plasma and depositing said copper onto the plaque.
- The plaque thus obtained will be hereinafter referred to as “Plaque 4C”.
- Example 5 – Surface analysis
- 5a – Surface analysis by ATR-FTIR
- Attenuated total reflection (ATR) is a sampling technique used in conjunction with infrared (IR) spectroscopy which enables samples to be examined directly in the solid or liquid state. Fourier transform infrared (FTIR) spectroscopy is a measurement technique that allows to record IR spectra.
- The surface of Plaque AP obtained after step (a) of Example 2 was analysed by ATR-FTIR, as follows.
- A piece measuring 20mm x 30mm of the treated plaque was subjected to measurements performed with Ge crystal, with a resolution of 2cm-1 and 256 scans.
- The same analysis was performed on the surface of Plaque 1C, obtained following the procedure disclosed in Example 1 and having the same measures of Plaque AP.
- The results were compared by performing spectral subtraction between the spectra obtained for Plaque AP and Plaque 1C, and weak positive bands were observed in the region at about 3300 cm-1 and from 1680 cm-1 to 1500 cm-1, which were compatible with the presence of chemical groups containing nitrogen atoms like amide, urethanes and ureas.
- The comparison of the peaks in the functional region of ATR-FTIR spectra is showed in Table 2.
Table 2 Plaque Positive peak at 3300 cm -1 Positive peaks between 1680 cm -1 and 1500 cm -1 1C(*) - - AP Compatible with N containing
groupsCompatible with N containing groups - (*) comparison
- The above results showed that atmospheric plasma treatment modified the surface of the elastomer plaque, by introducing nitrogen-containing groups.
- Example 5b - Surface analysis by X-Ray (XPS)
- X-ray Photoelectron Spectroscopy (XPS) is a surface analysis, which provides quantitative and chemical state information from the surface of the material being studied. The average depth of analysis was approximately 5 nm, so that it was possible to obtain the actual composition of the sample surface.
- The surface of Plaque 2 obtained after step (b) of Example 2 was analysed by XPS.
- The same analysis was performed on the surface of Plaque 1C, obtained following the procedure disclosed in Example 1.
- The comparison between Nitrogen, Palladium and Copper concentration observed on Plaque 1C and Plaque 2 is showed in Table 3.
Table 3 Plaque Atomic concentration (%) N Pd Cu 1C(*) 0% 0% 0% 2 1.32% 0.46% 4.77% - (*) comparison
- The above results showed that Plaque 2, which is an examples of the multilayer article according to the present invention, contains the nitrogen-containing groups, as well as palladium and copper atoms.
- Example 6 – Evaluation of adhesion of the metallic layer
- The adhesion of the metallic layer was evaluated on the following plaques:
- Plaque 2 obtained according to the procedure described in Example 2,
- Plaque 3C obtained according to the procedure described in Comparative Example 3 and
- Plaque 4C obtained according to the procedure described in Comparative Example 4. - The adhesion was evaluated as follows: using a cutting tool, two series of perpendicular cuts were performed on the metallic layer of Plaque 2, Plaque 3C and Plaque 4C, in order to create a lattice pattern on them. A piece of tape was then applied and smoothened over the lattice and removed with an angle of 180° with respect to the metallic layer.
- The adhesion of metallic layer was then assessed for Plaque 2, Plaque 3C and Plaque 4C by comparing the lattice of cuts with the ASTM D3359 standard procedure. The classification of test results ranged from 5B to 0B, whose descriptions are depicted in Table 4 herein below.
Table 4 ASTM D3359
ClassificationDescription 5B The edges of the cuts are completely smooth; none of the squares of the lattice is detached. 4B Detachment of flakes of the coating at the intersections of the cuts. A cross cut area not significantly greater than 5% is affected. 3B The coating has flaked along the edges and/or at the intersection of the cuts. A cross cut area significantly greater than 5%, but not significantly greater than 15% is affected. 2B The coating has flaked along the edges of the cuts partly or wholly in large ribbons, and/or it has flaked partly of wholly on different parts of the squares. A cross cut area significantly greater than 15%, but not significantly greater than 65%, is affected. 1B The coating has flaked along the edges of the cuts in large ribbons and/or some squares have detached partly or wholly. A cross cut area significantly greater than 35%, but not significantly greater than 65%, is affected. 0B Any degree of flaking that cannot be classified even by classification 1B. - The adhesion value obtained for the plaques was as follows:
- Plaque 2 = 5B;
- Plaque 3C = 1B;
- Plaque 4C = 1B - The above results demonstrated the excellent adhesion achieved in the elastomer article according to the present invention.
- Example 7 – Evaluation of mechanical properties
- The mechanical properties of Plaque 2 obtained according to the procedure described in Example 2 and Plaque 1C obtained according to the procedure described in Example 1 were evaluated with tensile tests following the DIN 53504 S2 standard procedure.
- The measured mechanical properties are showed in Table 5.
Table 5 Plaque 1C(*) Plaque 2 Stress at 20% of strain [MPa] 4.6 4.9 Stress at 50% of strain [MPa] 7.7 8.0 Stress at 100% of strain [MPa] 14.7 14.9 Stress at break [MPa] 20.5 22.1 Strain at break [%] 137 140 - (*) comparison
- By visual assessment made during and after the test, it was verified that the metal layer remained completely adherent to the surface of Plaque 2 and that it followed the elongation of the same.
- The above results demonstrated that the mechanical properties of Plaque 1C(*) comprising the pristine elastomer were not altered by the procedure described in Example 2 and that an excellent adhesion was achieved in multi-layered elastomer article according to the present invention.
Claims (14)
- A multi-layered article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S)] comprising:- nitrogen-containing groups [groups (N)] and- at least one layer [layer (L1)] adhered to said surface (S) comprising at least one metal compound [compound (M)].
- The multi-layered article according to claim 1, wherein said elastomer comprises recurring units derived from at least one at least one (per)fluorinated monomer and/or at least one hydrogenated monomer.
- The multi-layered article according to claim 2, wherein said at least one (per)fluorinated monomer is selected from the group comprising:- C3-C8 perfluoroolefins;- C2-C8 hydrogenated fluoroolefins;- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins;- CH2=CH-Rf0 wherein Rf0 is a C1-C6 (per)fluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups;- CH2=CFORf1, wherein Rf1 is a C1-C6 fluoro- or perfluoroalkyl group;- CF2=CFORf2, wherein Rf2 is a C1-C6 fluoro- or perfluoroalkyl group; or a C1-C12 oxyalkyl or a C1-C12 (per)fluorooxyalkyl group comprising one or more ether groups; or a group of formula -CF2ORf3 in which Rf3 is a C1-C6 fluoro- or perfluoroalkyl or a C1-C6 (per)fluorooxyalkyl group comprising one or more ether groups;- CF2=CFORf4, wherein Rf4 is a C1-C12 alkyl or (per)fluoroalkyl group; a C1-C12 oxyalkyl; or a C1-C12 (per)fluorooxyalkyl; said Rf4 comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;- fluorodioxoles; and- fluorosilanes.
- The multi-layered article according to claim 2, wherein said at least one hydrogenated monomers comprises non-fluorinated monomers selected from the group comprising: C2-C8 non-fluorinated olefins (OI); diene monomers; vinyl monomers; acrylic monomers; styrene monomers; and silicon-containing monomers.
- The multi-layered article according to claim 4, wherein said silicon-containing monomer comprises:- silane, such as CH2=CH2-Si(Rf4)3 wherein each of Rf4 is independently selected from H, F and C1-C3 alkyl;- siloxane of formula (R)3Si-O-Si(R)3 and (R)2Si(OH)2, wherein each R is independently selected from H, linear or branched alkyl groups having from 1 to 6 carbon atoms, preferably methyl group, or phenyl group.
- The multi-layered article according to any one of the preceding claims, wherein said groups (N) are grafted onto said surface (S).
- The multi-layered article according to any one of the preceding claims, wherein said compound (M) comprises at least one metal selected from the group consisting of: Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, Ga and alloys thereof.
- A method for manufacturing a multi-layered article, said method comprising the steps of:(i) providing an article made of an elastomeric composition [composition (C)] comprising at least one elastomer, said article having at least one surface [surface (S-1)];(ii) forming nitrogen-containing groups [groups (N)] on said at least one surface (S-1) so as to provide an elastomer article having at least one nitrogen-containing surface [surface (S-2)];(iii) contacting said at least one surface (S-2) with a first composition [composition (C1)] comprising at least one metallization catalyst, so as to provide an article having at least one surface [surface (S-3)] containing groups (N) and at least one metallization catalyst; and(iv) contacting said at least one surface (S-3) with a second composition [composition (C2)] containing at least one metal compound [compound (M1)], so as to provide a multi-layered article having at least one surface [surface (S)] comprising groups (N) and at least one layer (L1) adhered to said surface (S) comprising at least one metal compound (M).
- The method according to claim 8, wherein said step (ii) is performed by treating said surface (S-1) in the presence of a nitrogen-containing gas.
- The method according to claim 9, wherein said nitrogen-containing gas is preferably selected from N2, NH3 or mixtures thereof, optionally in admixture with nitrogen-free gas such as CO2 and/or H2.
- The method according to any one of claims 8 to 10, wherein said composition (C2) is an electroless metallization plating bath, comprising at least one compound (M1), at least one reducing agent, at least one liquid medium and, optionally, one or more additives.
- The method according to any one of claims 8 to 11, wherein said composition (C3) comprises at least one compound (M2), at least one metal halide and, optionally, at least one ionic liquid.
- The method according to any one of claims 8 to 12, wherein said steps (iii) and (iv) are performed as a single step [step (iii-D)].
- The method according to any one of claims 8 to 13, wherein said method comprises after step (iv), step (v) of applying a third composition [composition (C3)] containing at least one metal compound [compound (M2)] onto said surface (S).
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JP2006108314A (en) * | 2004-10-04 | 2006-04-20 | Kyocera Chemical Corp | Metal plated board, manufacturing method thereof, flexible printed wiring board, and multilayer printed wiring board |
JP2008308762A (en) * | 2007-05-17 | 2008-12-25 | Kimoto & Co Ltd | Material for forming electroless plating and method for manufacturing electrolessly plated non-electroconductive base material |
GB0713802D0 (en) * | 2007-07-17 | 2007-08-22 | Smith & Nephew | Coatings |
WO2012007374A1 (en) * | 2010-07-14 | 2012-01-19 | Solvay Solexis S.P.A. | Fluoroelastomer composition |
TWI523900B (en) * | 2010-07-20 | 2016-03-01 | 首威索勒希斯股份有限公司 | Fluoroelastomer composition |
JP4936344B1 (en) * | 2010-10-04 | 2012-05-23 | 邦夫 森 | Metal film forming method and product having metal film |
WO2012049093A1 (en) * | 2010-10-15 | 2012-04-19 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomers |
EP2518187A1 (en) * | 2011-04-26 | 2012-10-31 | Atotech Deutschland GmbH | Aqueous acidic bath for electrolytic deposition of copper |
WO2013101822A2 (en) | 2011-12-29 | 2013-07-04 | 3M Innovative Properties Company | Metallization of fluoroelastomer films |
CN105074536B (en) | 2013-03-29 | 2018-07-17 | 索尔维特殊聚合物意大利有限公司 | Reflection multilayer mirror assembly |
-
2015
- 2015-11-19 CN CN201580074021.0A patent/CN107208268A/en active Pending
- 2015-11-19 WO PCT/EP2015/077077 patent/WO2016079230A1/en active Application Filing
- 2015-11-19 KR KR1020177016435A patent/KR20170084290A/en not_active Application Discontinuation
- 2015-11-19 US US15/528,316 patent/US20170306496A1/en not_active Abandoned
- 2015-11-19 EP EP15795206.0A patent/EP3221491B1/en active Active
- 2015-11-19 JP JP2017526682A patent/JP6840074B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US20170306496A1 (en) | 2017-10-26 |
WO2016079230A1 (en) | 2016-05-26 |
EP3221491B1 (en) | 2021-04-07 |
JP6840074B2 (en) | 2021-03-10 |
JP2017536478A (en) | 2017-12-07 |
CN107208268A (en) | 2017-09-26 |
KR20170084290A (en) | 2017-07-19 |
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