WO2017157749A1 - Compositions multicouches - Google Patents

Compositions multicouches Download PDF

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Publication number
WO2017157749A1
WO2017157749A1 PCT/EP2017/055511 EP2017055511W WO2017157749A1 WO 2017157749 A1 WO2017157749 A1 WO 2017157749A1 EP 2017055511 W EP2017055511 W EP 2017055511W WO 2017157749 A1 WO2017157749 A1 WO 2017157749A1
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WO
WIPO (PCT)
Prior art keywords
layer
metal
polymer
mol
composition
Prior art date
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PCT/EP2017/055511
Other languages
English (en)
Inventor
Marco Apostolo
Gregory HARKNESS
Stefano Mauri
Andrea Vittorio ORIANI
Original Assignee
Solvay Specialty Polymers Usa, Llc
Politecnico Di Milano
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Solvay Specialty Polymers Usa, Llc, Politecnico Di Milano filed Critical Solvay Specialty Polymers Usa, Llc
Priority to CN201780030578.3A priority Critical patent/CN109154095A/zh
Priority to JP2018548659A priority patent/JP2019510136A/ja
Priority to EP17708832.5A priority patent/EP3430184A1/fr
Priority to US16/084,901 priority patent/US20190085460A1/en
Publication of WO2017157749A1 publication Critical patent/WO2017157749A1/fr

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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
    • 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
    • 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
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

Definitions

  • the present invention relates to a process for obtaining a multilayer
  • composition to a composition obtainable via such method and to an article comprising said composition.
  • plastics in place of metal parts enables the production of wares that are generally cheaper, thinner, lighter and easier to install.
  • plastic parts enhance design flexibility with respect to metal components and have no corrosion issues.
  • ABS acrylonitrile-butadiene-styrene
  • ABS plumbing fixtures may release organic compounds when in contact with hot water and do not meet the requirements of North America standard NSF/ANSI 61 and similar standards, which establish the limits for release of organic compounds in the drinking water.
  • plated ABS materials are not approved for the manufacturing of appliances for drinkable hot water and can only be used in limited applications such as shower handles and knobs, but not in faucets, valves and similar items that may be heated to temperatures of at least 50°C.
  • the material should be inert and possess excellent barrier properties also when used with hot water.
  • ASME A1 12.18.1 which set the requirements for adhesion of the coating layers, stability in thermal cycling tests resistance to agents such as corrosion (copper-accelerated acetic acid-salt spray test - CASS).
  • Aromatic polymers such as polysulphones and polyphenylene sulphides are potentially suitable materials for plumbing application as metal substitutes, however difficulties have been encountered to provide a reliable and efficient method to plate their external surface with a metal layer in order to obtain metallized items that do not delaminate at high temperatures and have acceptable appearance.
  • GB1 164845 describes a process for plating aromatic polymers
  • a first etching step using the aggressive chemical chromic acid that is preferably avoided due to its high toxicity for the environment and for human health.
  • US 4588623 discloses metal plated articles comprising a blend of a
  • poly(aryl ether) polymer a styrene and/or acrylic copolymer and a compatibilizing amount of a polyhydroxyether, that is manufactured via a process comprising etching with chromic acid.
  • WOOO/61831 describes an item such as a faucet comprising a polymeric substrate and an outer plating metallic layer, that is deposed on the polymeric substrate by thermally spraying, which in general involves health and safety issues, is difficult to perform effectively on non-planar surfaces and provides low degree of adhesion for substrates that are small or with small curves.
  • compositions comprising a polymeric material plated with a metallic layer that is suitable for applications such as the manufacturing of plumbing appliance and can be produced by a process that is safe and suitable for industrial scale.
  • the invention provides a process for the manufacturing of a multilayer composition comprising at least the following:
  • a polymeric layer (L1 ) that comprises, or consists of, an aromatic polymer selected from the group consisting of a poly(aryl ether sulfone) polymer (P1 ) and a polyarylene sulphide (P2) and has at least one surface (S1 );
  • MC v. reducing metal
  • LC2 liquid composition
  • step v forming by electroless deposition a layer [layer (L2)] onto the at least one treated surface obtained in step v, said layer (L2) comprising at least one metal compound [compound (M1 )] and metal (MC) in ionic form; vii. applying an additional layer (L3) comprising a metal (M2), equal to or different from (M1 ), directly on layer (L2); and, optionally,
  • the present invention provides a multilayer composition comprising at least the following:
  • a polymeric layer (L1 ) that comprises, or consists of, a poly(aryl ether sulfone) polymer (P1 ) or polyarylene sulphide (P2) comprising at least one surface (S1 );
  • a first metallic layer (L2) which adheres directly on at least the surface (S1 ) and comprises nickel/phosphorus alloy and at least another metal (MC)
  • a second metallic layer (L3) which adheres directly on the surface of (L2) that is not in contact with polymeric layer (L1 ), comprising a metal (M2).
  • the present invention further provides an article comprising the multilayer composition as defined above or obtainable via the above process.
  • the amount of a component in a composition is indicated as the ratio between the weight of the component and the total weight of the composition multiplied by 100 (also: "wt%").
  • layers are permanently attached to each other via their surfaces of contact, e.g. classified as 5B to 2B, preferably from 5B to 3B, in the crosscut test according to ASTM D3359, test method B.
  • multilayer compositions wherein a polymeric layer as described above for layer (L1) and a metallic layer are assembled by contacting, e.g. by pressing (a) and (b) together, without adhesion between the two layers are outside the context of this invention.
  • polyaromatic polymer layer as defined above is at least partially plated with a metallic layer manufactured via the process of the invention are resistant to delamination also when heated at temperatures higher than 50°C, have an excellent appearance and tactile feeling, are stable over time and are particularly suitable to be used in plumbing fixtures.
  • the metallic layer is applied to a surface that is pre-treated via a radio-frequency glow discharge process in the presence of an etching gas medium comprising a nitrogen-containing gas.
  • the term “glow discharge process” is intended to denote a process powered by a radio-frequency amplifier wherein a glow discharge is generated by applying a voltage between two electrodes in a cell containing an etching gas medium.
  • the glow discharge so generated is then typically transferred, commonly using a jet head, onto the surface of the material to be treated.
  • the material to be treated is put between the electrodes in the cell containing the etching gas medium, so that the generated glow discharge is directly in contact with the surface of the material to be treated.
  • the glow discharge process typically comprises grafting one or more
  • At least a portion of the surface of the polymeric layer (L1 ) in the process of the invention typically comprises one or more grafted functional groups advantageously obtainable by a glow discharge process.
  • the expression "at least a portion ", when referred to the surface comprising one or more grafted functional groups, is to be understood to mean that embodiments wherein the surface has portions on which no grafted functional group is present are still encompassed by the present invention. Nevertheless, it is generally understood that substantially the entire surface (S1 ) of the multilayer assembly of the invention comprises one or more grafted functional groups.
  • etching gas medium comprising nitrogen
  • a gas or a mixture of gases suitable for use in a glow discharge process wherein at least a portion of the gas is formed by a chemical species including at least one nitrogen atom.
  • the glow discharge process is typically carried out in the presence of an etching gas medium comprising at least one gas selected from the group consisting of N2, NH3, CH 4 , CO2, He, O2 and H2, and mixtures thereof.
  • the etching gas medium typically further comprises air.
  • the glow discharge process is preferably carried out in the presence of an etching gas medium comprising N2 and/or NH3, optionally, at least one gas selected from the group consisting of h and He and, optionally, air.
  • the etching gas medium typically comprises N2, preferably consists of:
  • the glow discharge process is typically carried out under reduced
  • the glow discharge process is preferably carried out under atmospheric pressure at about 760 Torr.
  • the glow discharge process may be carried out either under air or under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001 % v/v).
  • the glow discharge process is preferably carried out under air.
  • the glow discharge process is preferably carried out at a radio-frequency comprised between 1 kHz and 100 kHz.
  • the glow discharge process is preferably carried out at a voltage comprised between 1 kV and 50 kV.
  • the glow discharge process typically generates a plasma discharge.
  • the grafted functional groups that may be formed in the process typically comprise one or more atoms of the etching gas medium.
  • the grafted functional groups are preferably selected from the group consisting of N-containing functional groups.
  • S2a or (S2b) of the multilayer assembly of the invention can be determined according to any suitable techniques such as, for instance, FT-IR techniques, preferably Attenuated Total Reflectance (ATR) coupled to FT-IR techniques, or X-ray induced photoelectron spectroscopy (XPS) techniques.
  • suitable techniques such as, for instance, FT-IR techniques, preferably Attenuated Total Reflectance (ATR) coupled to FT-IR techniques, or X-ray induced photoelectron spectroscopy (XPS) techniques.
  • the so-treated polymeric surface advantageously maintains its bulk properties including its mechanical properties.
  • the inventors have also found that, after treatment by a glow discharge process using an etching gas medium, the metal layer is successfully adhered to the so-treated polymeric surface comprising or consisting of an aromatic polymer as defined above.
  • the process comprises
  • step (iii-a) of the process of the invention at least a portion of the surface (S1 a) or (S1 b) is coated by electroless deposition using a liquid composition [composition (LC1 )] comprising at least one metal salt
  • salt (M1 ) said salt (M1 ) being typically a salt of a compound (M1).
  • the liquid composition (LC1 ), as well as the other liquid compositions used in the context of the present invention, generally contains water and is preferably an aqueous composition wherein more than 50%, preferably more than 90%, of the liquid medium is water.
  • composition (LC1 ) comprising an electroless metallization catalyst that is least one metal salt of a metal (MC), wherein MC is preferably selected from platinum, palladium gold, silver, tin and their alloys.
  • MC is preferably selected from platinum, palladium gold, silver, tin and their alloys.
  • the salt of (MC) in composition (LC1 ) is a palladium (II) salt, typically PdC , optionally together with a tin salt.
  • alloy indicates a compound comprising a stable mixture of metals or a mixture of at least one metal and at least one non- metallic element, in any suitable weight ratio.
  • An alloy may be a solid solution of metal elements (a single phase) or a mixture of metallic phases (two or more solutions).
  • the expression "at least a portion ", when referred to the surface of the underlying layer coated with a metal layer, is to be understood to mean that embodiments wherein the underlying layer has portions of its surface on which no metal layer is adhered to are still encompassed by the present invention. Nevertheless, it is generally understood that substantially the entire surface of the underlying layer has adhered thereto a metal layer as defined above.
  • the amount of metal (MC) that is present in the compositions obtainable according to the method of the present invention is not particularly limited and, as anon-limiting example, it can range from 10-20 parts per million to 0.1 % based on the total weight of layer (L2).
  • the amount of (MC) can be determined via the techniques commonly used and known to the person skilled in the art such as atomic absorption, neutron activation, spectrophotometry, X-ray fluorescence, XPS, stripping voltammetry and similar methods.
  • the metal (M1 ) comprises copper, nickel, a nickel/phosphorous alloy, aluminium, silver, gold, and mixtures or alloys thereof.
  • the metal (M1 ) comprises copper or a nickel/phosphorous alloy.
  • the process according to the invention comprises step iii,
  • step ii. wherein the at least one etched surface (S2) obtained in step ii. is contacted with a composition (LC3) comprising a surfactant to obtain at least a pre-treated surface (S2a).
  • LC3 composition comprising a surfactant
  • surfactants are organic compounds that are amphiphilic, meaning they contain both hydrophobic groups and hydrophilic groups, hence they contain both a water-insoluble (or oil- soluble) component and a water-soluble component.
  • surfactants in the process of the invention are those of general formula (S)
  • (R SU rf) is a C2-C20 alkyl chain, linear, cyclic or branched, more preferably wherein (R SU rf) is a a C2-C8 alkyl chain. More preferably, the surfactant in (LC3) is ethanolamine.
  • (LC3) contains generally water and can contain water-miscible organic solvents such as acetone or alcohols, preferably ethanol, methanol or isopropyl alcohol, most preferably isopropyl alcohol.
  • (M1 ) is copper and the process comprises step iii. It was found that an improved adhesion of copper to the polymeric substrate (L1 ) is obtained when the surface is treated with solution (LC3) prior to electroless deposition.
  • composition (LC2) typically is water-based and can comprise at least one organic solvent [solvent (S)] and at least one reducing agent
  • the solvent (S) is typically selected from the group consisting of:
  • ether oxides more particularly, diethyl oxide, dipropyl oxide, diisopropyl oxide, dibutyl oxide, methylter- butylether, dipentyl oxide, diisopentyl oxide, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether benzyl oxide; dioxane, tetrahydrofuran (THF),
  • glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether,
  • glycol ether esters such as ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate,
  • alcohols such as methyl alcohol, ethyl alcohol, diacetone alcohol,
  • ketones such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone, isophorone, and
  • linear or cyclic esters such as: isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate, g-butyrolactone.
  • the agent (R) is typically selected from the group consisting of sodium
  • composition (LC1 ) is of major importance for the outcome of the plating process.
  • unsatisfactory adhesion was obtained when colloidal palladium was used instead of a palladium (II) salt in (LC1 ) and little or no electroless deposition of the metal layer on the polymeric layer (L1) was observed when neutral or acidic solutions containing Pd(ll) salts were used instead of (LC1 ) as defined above.
  • the multilayer composition of the present invention comprises a polymeric layer (L1 ) which comprises an aromatic polymer selected from the group consisting of a poly(aryl ether sulfone) polymer (P1 ) and a polyarylene sulphide (P2), and having at least one surface (S1 ).
  • L1 polymeric layer
  • P1 poly(aryl ether sulfone) polymer
  • P2 polyarylene sulphide
  • PAES polymer of which at least 50 mol. % of the recurring units are recurring units (RPAES) of formula (K), the mol. % being based on the total number of moles in the polymer:
  • R at each location, is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;
  • - T is selected from the group consisting of a bond and a group
  • Rj and Rk equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • Rj and Rk are methyl groups.
  • h is zero for each R.
  • the recurring units (RPAES) are units of formula ( ⁇ '):
  • RPAES recurring units of formula (K) or formula ( ⁇ ').
  • the poly(aryl ether sulfone) is a poly(biphenyl ether sulfone) (PPSU).
  • a poly(biphenyl ether sulfone) polymer is a polyarylene ether sulfone which comprises a biphenyl moiety.
  • Poly(biphenyl ether sulfone) is also known as polyphenyl sulfone (PPSU) and for example results from the condensation of 4,4'-dihydroxybiphenyl (biphenol) and 4,4'- dichlorodiphenyl sulfone.
  • a poly(biphenyl ether sulfone) denotes any polymer of which more than 50 mol. % of the recurring units are recurring units (Rppsu) of formula (L):
  • the PPSU polymer of the present invention can therefore be a
  • At least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % or all of the recurring units in the PPSU are recurring units (Rppsu) of formula (L).
  • Rppsu recurring units of formula (L)
  • the poly(biphenyl ether sulfone) (PPSU) is a copolymer, it can be made of recurring units (R*PPSU), different from recurring units (Rppsu), such as recurrin units of formula (M), (N) and/or (O):
  • the poly(biphenyl ether sulfone) (PPSU) can also be a blend of a PPSU homopolymer and at least one PPSU copolymer as described above.
  • the poly(biphenyl ether sulfone) can be prepared by any method known in the art. It can for example result from the condensation of 4,4'-dihydroxybiphenyl (biphenol) and 4,4'-dichlorodiphenyl sulfone. The reaction of monomer units takes place through nucleophilic aromatic substitution with the elimination of one unit of hydrogen halide as leaving group. It is to be noted however that the structure of the resulting poly(biphenyl ether sulfone) does not depend on the nature of the leaving group.
  • PPSU is commercially available as Radel® PPSU from Solvay Specialty
  • the weight average molecular weight of the present invention is the weight average molecular weight
  • Mw of the PPSU may be from 30,000 to 80,000 g/mol, for example from
  • the weight average molecular weight (Mw) of PPSU can be determined by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards.
  • GPC gel permeation chromatography
  • PAES poly(aryl ether sulfone)
  • PSU polysulfone
  • a polysulfone denotes any polymer of which more at least 50 mol. % of the recurring units are recurring units (Rpsu) of formula (N) :
  • the PSU polymer of the present invention can therefore be a
  • the poly(biphenyl ether sulfone) (PSU) is a copolymer, it can be made of recurring units (R*PSU), different from recurring units (Rpsu), such as recurring units of formula (L), (M) and/or (O) above described.
  • PSU is available as Udel® PSU from Solvay Specialty Polymers USA,
  • the weight average molecular weight Mw of the PSU may be from 30,000 to 80,000 g/mol, for example from 35,000 to 75,000 g/mol or from 40,000 to 70,000 g/mol.
  • the poly(aryl ether sulfone) is a poly(ether sulfone) (PES).
  • a poly(ether sulfone) denotes any polymer of which more at least 50 mol. % of the recurring units are recurring units (RPES) of formula (O) :
  • the PES polymer of the present invention can therefore be a
  • recurring units in the PES are recurring units (RPES) of formula (O).
  • the poly(ether sulfone) (PES) is a copolymer
  • it can be made of recurring units (R*PES), different from recurring units (RPES), such as recurring units of formula (L), (M) and/or (N) above described.
  • PES is available as Veradel® PESU from Solvay Specialty Polymers USA,
  • the weight average molecular weight (Mw) of PAES for example PPSU, PES and PSU, can be determined by gel permeation chromatography (GPC) using methylene chloride as a mobile phase (2x 5 ⁇ mixed D columns with guard column from Agilent Technologies ; flow rate:
  • the weight average molecular weight (Mw) can be any weight average molecular weight (Mw).
  • the PAES polymers have a glass transition temperature ("T g ”) of at least about 200° C, at least about 210° C, or at least about 220° C.
  • T g glass transition temperature
  • the glass transition temperature can be measured using differential scanning calorimetry ("DSC") using a ramp rate of 20° C/minute according to the ASTM D3418 standard.
  • the composition of the polymeric layer (L1 ) include no more than about 98.5 weight percent ("wt.%") or no more than about 98 wt.% of the PAES polymer.
  • the polymer compositions comprises at least about 50 wt.%, at least about 55 wt.% or at least about 60 wt.% of the PAES polymer.
  • the PSU polymer is present in a concentration of more than about 1 wt.%, at least 1.5 wt.% or at least 2 wt.%. In some such embodiments, the PSU polymer concentration is no more than about 40 wt.%, no more than about 35 wt.% or no more than about 30 wt.%.
  • the total concentration of PSU and PPSU polymer can be more than about 1 wt.%. In such embodiments, the total concentration of the PSU and PPSU polymer is no more than about 40 wt.%, no more than about 35 wt.% or no more than about 30 wt.%.
  • the PPSU polymer is present in a
  • the PPSU polymer concentration is no more than about 40 wt.%, no more than about 35 wt.% or no more than about 30 wt.%.
  • the PPSU polymer concentration is more than about 1 wt.% and the PPSU polymer concentration is no more than about 40 wt.%, no more than about 35 wt.% or no more than about 30 wt.%.
  • the polymeric layer (L1 ) comprises a poly(arylene sulfide) polymer (P2).
  • P2 poly(arylene sulfide) polymer
  • the term "poly(arylene sulfide) polymer” is intended to denote any polymer comprising recurring units wherein more than 50% by moles of said recurring units are recurring units (RPAS) of formula (L):
  • Ar denotes an aromatic moiety comprising at least one aromatic mono- or poly-nuclear cycle, such as a phenylene or a naphthylene group, which is linked by each of its two ends to two sulfur atoms forming sulfide groups via a direct C-S linkage.
  • the aromatic moiety Ar may be unsubstituted (i.e. a phenyl group) substituted by one or more substituent groups, including but not limited to halogen atoms, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy groups, and C6-C18 aryloxy groups, and substituted or unsubstituted arylene sulfide groups, the arylene groups of which are also linked by each of their two ends to two sulfur atoms forming sulfide groups via a direct C-S linkage thereby creating branched or cross-linked polymer chains.
  • substituent groups including but not limited to halogen atoms, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy
  • recurring units in the PAS are recurring units (RPAS) of formula (L).
  • the mol. % are based on the total number of moles in the PAS.
  • the polymer (PAS) contains no recurring units other than recurring units (RPAS) of formula (L).
  • aromatic moiety Ar is preferably selected from the group consisting of those of formulae (X-A) to (X-K) here below:
  • Ri and R2 are selected from the group consisting of hydrogen atoms, halogen atoms, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy groups, and C6-C18 aryloxy groups, and substituted or unsubstituted arylene sulfide groups, the arylene groups of which are also linked by each of their two ends to two sulfur atoms forming sulfide groups via a direct C-S linkage thereby creating branched or cross-linked polymer chains.
  • the polymer may be a homopolymer or a copolymer such as a random copolymer or a block copolymer.
  • the polymer (PAS) can comprise one or more branched or cross-linked recurring units selected from the group consisting of those of
  • the PAS is a
  • polyphenylene sulfide polymer PPS
  • PPS polyphenylene sulfide polymer
  • Ri and R2 are selected from the group consisting of hydrogen atoms, halogen atoms, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy groups, and C6-C18 aryloxy groups, and substituted or unsubstituted arylene sulfide groups, the arylene groups of which are also linked by each of their two ends to two sulfur atoms forming sulfide groups via a direct C-S linkage thereby creating branched or cross-linked polymer chains.
  • the polyphenylene sulfide polymer denotes any polymer of which at least 50 mol. % of the recurring units are recurring units (Rpps) of formula (U) wherein Ri and R2 are hydrogen atoms.
  • the PPS polymer is such that at least about 60 mol.
  • recurring units in the PPS are recurring units (Rpps) of formula (U) wherein Ri and R2 are hydrogen atoms.
  • the PPS polymer is such that about 100 mol. % of the recurring units are recurring units (Rpps) of formula (!_'):
  • Ri and R2 are selected from the group consisting of hydrogen atoms, halogen atoms, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy groups, and C6-C18 aryloxy groups, and substituted or unsubstituted arylene sulfide groups, the arylene groups of which are also linked by each of their two ends to two sulfur atoms forming sulfide groups via a direct C-S linkage thereby creating branched or cross-linked polymer chains, or
  • Ri and R2 are hydrogen atoms.
  • the PPS polymer consists essentially of recurring units (Rpps) of formula (U).
  • PPS is notably manufactured and sold under the trade name Ryton ® PPS by Solvay Specialty Polymers USA, LLC.
  • the weight average molecular weight of the PPS may be from 30,000 to 70,000 g/mol, for example from 35,000 to
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) using ASTM D5296 with
  • PVDF polyvinylidene fluoride
  • the polymer composition of layer (L1 ) can include one or more additives.
  • Additives can include, but are not limited to, fillers, heat stabilizers, plasticizers, lubricants, processing aids, impact modifiers, flame retardants and antistatic agents.
  • the polymer composition includes a filler.
  • Desirable fillers include, but are not limited to, glass fibers, carbon fibers, graphite fibers, silicon carbide fibers, aramide fibers, wollastonite, talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, boron nitride, aluminum oxide. Fillers improve possibly notably
  • the polymer composition can have a total filler concentration of from about 1 wt.% to no more than about 40 wt.%, no more than about 30 wt.%, no more than about 25 wt.%, or no more than about 20 wt.%.
  • a person of ordinary skill in the art will recognize additional filler
  • a particularly desirable class of fillers include clay mineral fillers.
  • Clay mineral fillers include, but are not limited to, kaolin, mica and montmorillonite. Excellent results were obtained with kaolin.
  • the polymer compositions can have a clay mineral filler concentration of at least about 1 wt.%, at least about 5 wt.%, at least about 7 wt.%, at least about 8 wt.%, at least about 9 wt.% or at least about 10 wt.%.
  • the polymer composition can have a clay mineral filler concentration of no more than about 40, no more than about 30 wt.%, no more than about 20 wt.%, or no more than about 15 wt.%.
  • a clay mineral filler concentration of no more than about 40, no more than about 30 wt.%, no more than about 20 wt.%, or no more than about 15 wt.%.
  • the layer of metal (M2), and optionally that of metal (M3), can be deposed via an electroless method or via electrodeposition, according to any of the methods known to the person skilled in the art.
  • the process of the invention provides a cost-effective method for the production of metal-plated compositions comprising an aromatic polymer layer, that is suitable for industrial scale production.
  • the present invention provides a multilayer composition
  • the metal (M1) is a nickel/phosphorus alloy or copper.
  • the average thickness of layer (L2) and/or of layer (L3) is from 50 nanometers to 150 micrometers, preferably from 70 nanometers to 50 micrometers, more preferably from 100 nanometers to 10 micrometers, even more preferably from 0.5 to 5 micrometers or from 1 to 3 micrometers.
  • nickel/phosphorus alloy that have superior resistance to abrasion, to delamination of the metal layer at temperatures above 50°C and improved aesthetics with respect to electroless copper-plated items.
  • the present invention provides a multilayer composition comprising at least the following:
  • a polymeric layer (L1 ) that comprises, or consists of, a poly(aryl ether) polymer (P1 ) or polyarylene sulphide (P2) comprising at least one surface (S1 );
  • a first metallic layer (L2) which adheres directly on at least the surface (S1 ) and comprises nickel/phosphorus alloy and from 0.001 to 10% in weight based on the total weight of (L2) of a metal (MC);
  • a second metallic layer (L3) which adheres directly on the surface of (L2) that is not in contact with polymeric layer (L1 ), comprising a metal (M2).
  • Copper electroless deposition has been described for plating the aromatic polymers surface obtained after etching.
  • nickel- phosphorus alloys have been established as the preferred choice for plating ABS substrates in view of several advantages. Firstly, nickel in mixture with phosphorus is cheaper and more resistant to corrosion and abrasion than copper and may provide a better adhesion and improved aesthetics in some applications. Additionally, electroless deposition solutions of copper salts tend to degrade rapidly and need to be carefully formulated, hence they are not suitable for industrial scale applications, whereas nickel-hypophosphite solutions may have a useful life in a bath over more than six months.
  • the phosphorus/nickel alloy in the composition of the invention contains from 1 to 15% in weight based on the total weight of the composition of phosphorus.
  • the average thickness of layer (L2) and/or of layer (L3) is from 50 nanometers to 150 micrometers, preferably from 70 nanometers to 50 micrometers, more preferably from 100 nanometers to 10 micrometers, even more preferably from 0.5 to 5 micrometers or from 1 to 3 micrometers.
  • the polymer of layer (L1) is a polyarylene sulphide (P2), more preferably a polyphenylene sulphide (PPS) as defined above.
  • the multilayer composition according to the invention is preferably, the multilayer composition according to the invention
  • the present invention provides an article comprising the multilayer
  • the article according to the invention is in the form of a
  • plumbing fixture such as a faucet, a stop valve and related pieces of equipment such as ball valves, fittings, pumps, zone valves, manifolds, handles, tubing for heating and for plumbing.
  • the present invention provides a method for
  • the means for directing water comprise, or consist of, a composition as described above.
  • the water is drinking water.
  • the temperature of the water that is directed according to the method of the invention is not particularly limited and can range from 5°C to 90°C.
  • the means for directing water that comprise, or consist of, the composition as described above are in the form of a pipe, of a stop valve, of a faucet, or of a circuit that comprises all or at least a part of said elements.
  • the circuit can be in the form of a household plumbing system.
  • Polymeric substrate UDEL ® PSU P 1700 NT (polymer P1 ) supplied by Solvay Specialty Polymers USA L.L.C.
  • the treated surface of the (P1 ) sample obtained according to Step 1 -A was immersed in an aqueous solution containing Ethanolamine (20% w/w) and Isopropyl alcohol (1 % w/w) for 3 minutes.
  • the treated surface Prior to nickel deposition, the treated surface was activated by immersion in an aqueous solution containing 80 mg/L of colloidal palladium and 100 ml/L HCI for 4 minutes, resulting in the treated surface of the Udel® sample being entirely coated with Pd particles at a high density deriving from colloidal palladium.
  • the so activated surface of the Udel® sample was then immersed in an aqueous plating bath containing 90 g/L of NiSO 4 , boric acid and organic additives.
  • the plating temperature was 40°C and its pH value was 9. Nickel coating thus obtained was found to be partially detached
  • Example 3 Manufacture of a sample without surface cleaning step
  • a Udel® sample was treated following step 1 -A and 1 -C without surface cleaning with solution (LC1 ) according to the invention (step 1 -B) in order to evaluate how surface cleaning influences adhesion behaviour.
  • Adhesion measured on this sample was significantly lower in respect of sample obtained according to Example 1 that comprises the treatment with composition (LC1 ).
  • Example 4 Chromium finishing of nickel plated sample
  • Sample obtained according to Example 1 was coated with metallic chromium by electrodeposition plating. Prior to chromium deposition, the sample was coated with copper and nickel in order to increase metallic thickness and to minimize internal stresses.
  • the adhesion strength between the metallic layer (Mc) and the layer (Pc) of the tube of the multilayer tubular articles of the invention was measured according to ASTM D3359 standard procedure. Using a cutting tool, two series of perpendicular cuts were performed on the metallic layer of the tapes obtained according to either Example 1 or Example 2 thereby providing a lattice pattern thereon. A piece of an adhesive label was then applied over the lattice and removed with an angle of 180° with respect to the metallic layer.
  • test results ranged from 5B to 0B, whose descriptions are depicted in Table 1 here below:
  • 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.
  • the coating has flaked along the edges of the cuts in large ribbons and/or some squares have detached partly or wholly.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un procédé d'obtention d'une composition multicouches, une composition pouvant être obtenue par ledit procédé et un article comprenant ladite composition. Le procédé comprend au moins les étapes suivantes : i) la fourniture d'une couche polymère (L1) comprenant un polymère aromatique sélectionné dans le groupe constitué par un polymère poly(aryl éther sulfone) (P1) et un sulfure de polyarylène (P2), et présentant au moins une surface (S1) ; ii) le traitement d'au moins la surface (S1) de (L1) par un procédé de décharge luminescente à radiofréquence en la présence d'un milieu gazeux de gravure comprenant un gaz contenant de l'azote pour obtenir une surface gravée (52) ; iii) éventuellement, la mise en contact de la surface gravée (S2) obtenue à l'étape ii) avec une composition (LC3) comprenant un agent de surface pour obtenir au moins une surface pré-traitée (S2a) ; iv) la mise en contact de la surface gravée (S2) obtenue à l'étape ii) ou de la surface pré-traitée (S2a) obtenue à l'étape iii) avec une composition liquide (LC1) comprenant au moins un métal (MC) sous forme ionique et présentant un pH supérieur ou égal à 9,0, de façon à fournir un article présentant au moins une surface (S-3) traitée avec une composition contenant du métal (MC) sous forme ionique ; v) la réduction d'un métal (MC) sous forme ionique sur la surface (S-3) à sa forme métallique par mise en contact de (S-3) avec une composition liquide (LC2) contenant un agent réducteur ; vi) la formation par dépôt autocatalytique d'une couche (L2) sur ladite/lesdites surface(s) traitée(s) obtenue(s) à l'étape v), ladite couche (L2) comprenant au moins un composé métallique (M1) et un métal (MC) sous forme ionique ; vii) l'application d'une couche supplémentaire (L3) comprenant un métal (M2), identique ou différent de (M1), directement sur la couche (L2) ; et, optionnellement viii) l'application d'une couche supplémentaire (L4) d'un métal (M2) sur (L3).
PCT/EP2017/055511 2016-03-17 2017-03-09 Compositions multicouches WO2017157749A1 (fr)

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CN201780030578.3A CN109154095A (zh) 2016-03-17 2017-03-09 多层组合物
JP2018548659A JP2019510136A (ja) 2016-03-17 2017-03-09 多層組成物
EP17708832.5A EP3430184A1 (fr) 2016-03-17 2017-03-09 Compositions multicouches
US16/084,901 US20190085460A1 (en) 2016-03-17 2017-03-09 Multilayer compositions

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US201662309749P 2016-03-17 2016-03-17
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1164845A (en) 1965-08-20 1969-09-24 Union Carbide Corp Process for Metal Plating Aromatic Polymer
US4107147A (en) * 1977-09-02 1978-08-15 General Electric Company Polysulfoneimides
US4588623A (en) 1984-09-28 1986-05-13 Union Carbide Corporation Metal plated poly(aryl ether) containing articles
US5180639A (en) * 1990-10-26 1993-01-19 General Electric Company Method of preparing polymer surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom
US20050233148A1 (en) * 2002-06-06 2005-10-20 Antoine Fares-Karam Metallised parts made from plastic material
US20070224346A1 (en) * 2006-03-22 2007-09-27 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
WO2016097329A1 (fr) * 2014-12-19 2016-06-23 Solvay Specialty Polymers Italy S.P.A. Procédés de production d'articles tubulaires multicouches

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1164845A (en) 1965-08-20 1969-09-24 Union Carbide Corp Process for Metal Plating Aromatic Polymer
US4107147A (en) * 1977-09-02 1978-08-15 General Electric Company Polysulfoneimides
US4588623A (en) 1984-09-28 1986-05-13 Union Carbide Corporation Metal plated poly(aryl ether) containing articles
US5180639A (en) * 1990-10-26 1993-01-19 General Electric Company Method of preparing polymer surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom
US20050233148A1 (en) * 2002-06-06 2005-10-20 Antoine Fares-Karam Metallised parts made from plastic material
US20070224346A1 (en) * 2006-03-22 2007-09-27 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
WO2016097329A1 (fr) * 2014-12-19 2016-06-23 Solvay Specialty Polymers Italy S.P.A. Procédés de production d'articles tubulaires multicouches

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