WO2016079230A1 - Multi-layered elastomer article and method for making the same - Google Patents
Multi-layered elastomer article and method for making the same Download PDFInfo
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- WO2016079230A1 WO2016079230A1 PCT/EP2015/077077 EP2015077077W WO2016079230A1 WO 2016079230 A1 WO2016079230 A1 WO 2016079230A1 EP 2015077077 W EP2015077077 W EP 2015077077W WO 2016079230 A1 WO2016079230 A1 WO 2016079230A1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- 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)].
(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).
- 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.
- 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.
- 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.
(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.
(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 patents
(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, in
(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 patents
- 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, patents
- alkali metal or alkaline-earth metal iodides and/or bromides, such as described notably in patent
(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 %.
- 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.
- 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.
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
Ingredients | Amount (phr) |
Tecnoflon® PL855 | 100 |
Carbon Black N990 | 30 |
ZnO | 5 |
Luperox® 101XL45 | 3 |
TAIC | 4 |
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
Plaque | Positive peak at 3300 cm -1 | Positive peaks between 1680 cm -1 and 1500 cm -1 |
1C(*) | - | - |
AP | Compatible with N containing groups | Compatible with N containing groups |
Plaque | Atomic concentration (%) | ||
N | Pd | Cu | |
1C(*) | 0% | 0% | 0% |
2 | 1.32% | 0.46% | 4.77% |
- 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.
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. |
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. |
- Plaque 2 = 5B;
- Plaque 3C = 1B;
- Plaque 4C = 1B
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 |
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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EP15795206.0A EP3221491B1 (en) | 2014-11-20 | 2015-11-19 | Multi-layered elastomer article and method for making the same |
KR1020177016435A KR20170084290A (en) | 2014-11-20 | 2015-11-19 | Multi-layered elastomer article and method for making the same |
US15/528,316 US20170306496A1 (en) | 2014-11-20 | 2015-11-19 | Multi-layered elastomer article and method for making the same |
JP2017526682A JP6840074B2 (en) | 2014-11-20 | 2015-11-19 | Multi-layer elastomer article |
CN201580074021.0A CN107208268A (en) | 2014-11-20 | 2015-11-19 | Multilayer elastomeric product and its manufacture method |
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EP14193990.0 | 2014-11-20 | ||
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EP (1) | EP3221491B1 (en) |
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CN109576684A (en) * | 2019-01-29 | 2019-04-05 | 上海交通大学 | A kind of method of polymeric film surface chemical plating |
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CN109476110A (en) * | 2016-07-26 | 2019-03-15 | 索尔维特殊聚合物意大利有限公司 | Fuel hose |
WO2018019754A1 (en) | 2016-07-28 | 2018-02-01 | Solvay Specialty Polymers Italy S.P.A. | Electric circuit including a flexible conductor |
CN109792837A (en) * | 2016-07-28 | 2019-05-21 | 索尔维特殊聚合物意大利有限公司 | Circuit including fexible conductor |
WO2018193029A1 (en) | 2017-04-21 | 2018-10-25 | Solvay Specialty Polymers Italy S.P.A. | Article and method for its manufacture |
CN110678578A (en) * | 2017-04-21 | 2020-01-10 | 索尔维特殊聚合物意大利有限公司 | Article and method of making the same |
JP2020517493A (en) * | 2017-04-21 | 2020-06-18 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | Article and manufacturing method thereof |
CN109576684A (en) * | 2019-01-29 | 2019-04-05 | 上海交通大学 | A kind of method of polymeric film surface chemical plating |
Also Published As
Publication number | Publication date |
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US20170306496A1 (en) | 2017-10-26 |
EP3221491B1 (en) | 2021-04-07 |
JP6840074B2 (en) | 2021-03-10 |
JP2017536478A (en) | 2017-12-07 |
EP3221491A1 (en) | 2017-09-27 |
CN107208268A (en) | 2017-09-26 |
KR20170084290A (en) | 2017-07-19 |
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