WO2020201387A1 - A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization - Google Patents
A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization Download PDFInfo
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- WO2020201387A1 WO2020201387A1 PCT/EP2020/059313 EP2020059313W WO2020201387A1 WO 2020201387 A1 WO2020201387 A1 WO 2020201387A1 EP 2020059313 W EP2020059313 W EP 2020059313W WO 2020201387 A1 WO2020201387 A1 WO 2020201387A1
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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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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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
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
Definitions
- the present invention relates to the activation of surfaces of typically non-conductive or car bon-fibres containing substrates for subsequent metallization.
- the present invention relates to a method for activating a surface of a non- conductive or carbon-fibres containing substrate for metallization, a method for metallizing an activated surface of a non-conductive or carbon-fibres containing substrate, a method for preparing an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization, and an aqueous, pal ladium-free activation composition for activating a surface of a non-conductive or carbon- fibres containing substrate for metallization.
- a metallization of typically such substrates is commercially of high interest.
- such substrates are covered with structures or layers of metal, either for decora tive or functional applications.
- typically non-conductive plastic substrates are used to manufacture sanitary articles with a shiny chromium layer.
- chromium covered plastic substrates are used in the automotive industry.
- a functional metallization is essential in for example man ufacturing printed circuit boards.
- a non-conductive resin-containing laminate is used as a base material usually harboring a circuitry of copper lines.
- Carbon-fibres containing substrates experience an increasing potential as catalytically ac- tive surfaces in e.g. power-to-gas, power-to-fuel, and power-to-chemicals applications, and batteries.
- a cleaning of the surface of the non-conductive or carbon-fibres con- taining substrate is carried out, e.g. to remove grease or impurities.
- a pre-treatment or conditioning of said surface is conducted in order to make the surface receptive to the following activation.
- a pre-treatment for example includes in some cases an etching in order to create pores and to enlarging the surface.
- the important activation is carried out.
- a very thin seed or activation layer is deposited/anchored on the surface of the non-conductive or car bon-fibres containing substrate, serving as starting point for a subsequent first metallization layer.
- the seed or activation layer usually serves as mediator between said surface of the non-conductive or carbon- fibres containing substrate and the one or more following metallization layers.
- the seed/activation layer is formed by depositing metal nanoparticles on said surface, for exam ple from a colloidal activation composition.
- said first metallization layer is deposited on the seed/activation layer, most commonly by electroless plating.
- this electroless plating includes an immersion-type plating, i.e. a deposition of a more noble metal on the seed/activation layer by means of exchange reaction and in absence of a reducing agent.
- it in cludes a deposition of a metal or metal alloy through autocatalytic deposition, which means a deposition facilitated by means of a reducing agent.
- a second metallization layer is deposited on the first metallization layer, either again by autocatalytic deposition or by electrolytic deposition.
- CN 107460459 A relates to simple nano-copper activation liquid utilizing sta bilizers and reducing agents to prevent agglomeration and oxidation, respectively, of the nanoparticles.
- US 4,278,712 discloses a method for the activation of a weakly active colloidal dispersion useful in the preparation of non-conductors prior to electroless plating.
- the method is based upon controlled oxidation of otherwise weakly active colloids by treatment with suitable gases and/or chemical agents, which render said controlled oxidation.
- suitable gases and/or chemical agents which render said controlled oxidation.
- the pres ence of at least one colloid stabilizer is mandatory. In this way a reversible equilibrium is not maintained.
- the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
- the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles, and
- oxidation is advantageously utilized, necessary, and con sidered to be of great benefit. It turned out, contrary to common thinking, that it is not nec- essary to maintain the particles for a long time in a respective activation composition.
- a respec tive activation composition is easily set up/activated at the place where it is needed by simply adding the required reducing agent.
- product delivery time is irrelevant for the life time of the product/method.
- the present invention relies on the fact, that the particles are formed again and again in situ, which renders any stabilization or stabilizer compounds obsolete.
- the dissolved transition metal ions and the metal particles thereof are present in a reversible equilibrium.
- a very effective and strong activation can be achieved because fresh particles without a shell of stabilizer compounds around them are formed with a relatively short life time. Subsequently, they are reacted back into their ionic form by oxidation. Upon adding further reducing agent fresh particles are formed again, i.e. in situ.
- a transition metal or a transition metal alloy is deposited on the surface of said substrate and an activated surface for subsequent metallization is obtained.
- concentration of dissolved metal ions of the first species decreases over time due to deposition.
- replenishment of the first spe cies is easily achieved by simply adding ions of that species. Therefore, replenishment is extremely easy and simple. This furthermore, significantly increases the life time of a re spective activation composition and a thereto related method.
- the respective method and activation composition does not necessarily require expensive noble metals but can be carried out with low-priced transition metals.
- the interruptions are in some cases longer than the time during the action is carried out. It includes even only temporary and brief actions.
- “species” de notes a chemical element.
- “a first species of dissolved transition metal ions” denotes dissolved metal ions of a transition metal element of groups 3 to 12 of the periodic table, e.g. copper.
- a first species of dissolved transition metal ions and additionally metal particles thereof denotes dissolved metal ions of this first species and additionally metal particles of this first species, e.g. in the aqueous, palladium-free activation composition.
- step (a) of the method of the present invention for activating, a non-conductive or carbon- fibres containing substrate with a surface is provided.
- a substrate inherently cannot be successfully metallized and therefore needs an activation.
- activating means to modify the surface of the non- conductive or carbon-fibres containing substrate in such a way that it comprises the transi tion metal or transition metal alloy after the respective activation step with sufficient adhesion for subsequent metallization. Furthermore, the deposited transition metal and transition metal alloy, respectively, is sufficiently adherent to the surface such that a subsequent met- allization layer (i) can be deposited thereon and (ii) is altogether also sufficiently adherent to the surface of the non-conductive or carbon-fibres containing substrate.
- the non-conductive substrate comprises, preferably is, selected from the group consisting of plastics, resin-con taining laminates, glasses, ceramics, semi-conductors, and mixtures thereof.
- Preferred plastics comprise, preferably are, thermoplastics, more preferably comprise, pref erably are, polyacrylates, polyamides, polyimides, polyesters, polycarbonates, poly- alkylenes, polyphenylenes, polystyrenes, polyvinyls, or mixtures thereof.
- Preferred polyacrylates comprise poly(methyl methacrylate) (PMMA).
- Preferred polyimides comprise polyetherimide (PEI).
- Preferred polyesters comprise polylactic acid (PLA).
- Preferred polycarbonates comprise polycarbonate obtained with bisphenol A (PC).
- Preferred polyalkylenes comprise polyethylene (PE), polypropylene (PP), polytetrafluoroeth- ylene (PTFE), polyoxymethylene (POM), or mixtures thereof.
- Preferred polyphenylenes comprise poly(phenylene oxide) (PPO), poly(phenylene ether) (PPE), or mixtures thereof.
- Preferred polystyrenes comprise polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene/butadiene rubber (SBR), styrene-acrylonitrile (SAN).
- PS polystyrene
- ABS acrylonitrile butadiene styrene
- SBR styrene/butadiene rubber
- SAN styrene-acrylonitrile
- Preferred polyvinyls comprise polyvinyl chloride (PVC), poly(ethylene-vinyl acetate) (PEVA), polyvinylidene difluoride (PVDF), or mixtures thereof.
- PVC polyvinyl chloride
- PEVA poly(ethylene-vinyl acetate)
- PVDF polyvinylidene difluoride
- Preferred resin-containing laminates comprise, preferably are, fiber-enforced resin-contain ing laminates, most preferably glass-fiber-enforced laminates.
- the resin-containing laminates comprise as resin one or more than one polymer of epoxys, vinylesters, polyesters, amides, imides, phenols, alkylenes, sulfones, or mixtures thereof, most preferably epoxy, imides, or mixtures thereof.
- a very preferred resin-containing laminate comprises, preferably is, FR4.
- Preferred glasses comprise, preferably are, silica glass, soda-lime glass, float glass, fluoride glass, aluminosilicate glass, phosphate glass, borate glass, borosilicate glass, chalcogenide glass, aluminium oxide glass, or mixtures thereof.
- Preferred ceramics comprise, preferably are, glass-ceramics, aluminium oxide ceramics, or mixtures thereof.
- Preferred semi-conductors comprise, preferably are, silicon-based semi-conductors, more preferably silicon-based semi-conductors comprising silicon dioxide and/or silicon.
- Very preferred semi-conductors are wafers.
- the carbon-fibres containing substrate comprise, preferably are, carbon-fibre composites and/or arrange ments of carbon-fibre filaments.
- Preferred carbon-fibre composites comprise, preferably are, carbon-fibre reinforced poly mers and/or carbon-fibre containing fabrics, more preferably carbon-fibre reinforced poly mers and/or woven carbon-fibre containing fabrics.
- Preferred arrangements of carbon-fibre filaments comprise, preferably are, fabrics made of carbon-fibres, most preferably woven fabrics made of carbon-fibres.
- An in particularly preferred carbon-fibres containing substrate is a carbon-fibre containing felt.
- a pre-treatment of the surface of the non-conductive or carbon-fibres con taining substrate is preferred.
- a method of the present invention comprising a pre-treatment step for the substrate prior to step (c):
- the nitrogen-containing compound is a polymer comprising pyrrolidine moie ties.
- the polymer is cationic.
- the nitrogen-containing compound consists of carbon atoms, nitrogen atoms, and hydrogen atoms.
- the nitrogen- containing compound comprises, preferably is, Polyquaternium 6.
- step (a-1) is carried out for 1 minute to 10 minutes, preferably for 2 minutes to 8 minutes, more preferably for 3 minutes to 6 minutes, most preferably for 3.5 minutes to 5 minutes.
- the aqueous, palladium-free activation composition is aqueous, palladium-free activation composition:
- step (b) of the method of the present invention for activating, an aqueous, palladium-free activation composition is provided.
- the aqueous composition utilized in the method of the present invention is an aqueous composition, which means that water is the primary component.
- more than 50 wt.-% of the composition is water, based on the total weight of the aqueous composition, preferably at least 70 wt.-%, even more preferably at least 90 wt.-%, most preferably 95 wt- % or more.
- the composition comprises one or more than one solvent (other than water) that is miscible with water.
- most preferred is a method, wherein water is the only solvent, and, thus, most preferably the composition is substantially free of or does not comprise organic solvents at all.
- the term“substantially free of or does not comprise” of a subject-matter independently denotes that said subject-matter is not present at all (“does not comprise”) or is present only in (to) a very little and undisturbing amount (extent) without affecting the intended purpose of the invention (“substantially free of”).
- a subject-matter e.g. a compound, a chemical, a material, etc.
- such a subject-matter might be added or utilized unintentionally, e.g. as unavoidable impurity “substantially free of or does not com prise” preferably denotes 0 (zero) ppm to 5 ppm, based on the total weight of e.g.
- the acti vation composition preferably 0 ppm to 3 ppm, more preferably 0 ppm to 1.5 ppm, even more preferably 0 ppm to 1 ppm, most preferably 0 ppm to 0.5 ppm, even most preferably 0 ppm to 0.1 ppm.
- This principle applies likewise to other subject-matters, e.g. to the total weight of the transition metal or transition metal alloy obtained in step (c) of the method of the present invention (for activating).
- the activation composition has an acidic pH, a neutral pH, or an alkaline pH, preferably an acidic or neutral pH, most preferably an acidic pH.
- a method of the present invention (for activating) is preferred, wherein the pH of the activation composition is in a range from 3 3.0 to £ 6.5, preferably in a range from 3 4.0 to £ 6.0.
- the one or more than one reducing agent comprises a borohydride.
- the pH in the activation composition is typically a result of the presence of (i) to (iv). If an adjustment of the pH is necessary, it is carried out by typical means.
- Preferred acids are mineral acids and organic acids.
- a preferred mineral acid is sulfuric acid.
- a preferred organic acid is the acid form of the one or more than one complexing agent.
- a preferred alkaline compound is an alkaline hydroxide, preferably NaOH, an alkaline carbonate, preferably so dium carbonate, and ammonia.
- the pH is determined at a temperature of 20°C, i.e. the defined pH is referenced to 20°C.
- the activation composition has a temperature of 20°C. This does not mean that the activation composition in itself is limited to the specific temperature of 20°C. For preferred temperatures of the acti vation composition see below.
- the aqueous composition utilized in the method of the present invention is palladium-free. Therefore, the activation composition is substantially free of or does not com prise palladium ions. This means that neither compounds comprising palladium are present nor palladium atoms/particles or palladium ions.
- the present invention is an excellent alternative to palladium-containing activation processes with identical or at least al most identical results in terms of activation.
- the activation composition is substantially free of or does not comprise platinum ions, gold ions, silver ions, rhodium ions, ruthenium ions, and iridium ions, preferably is substan tially free of or does not comprise platinum, gold, silver, rhodium, ruthenium, and iridium.
- the aqueous composition utilized in the method of the present invention (for activating) com prises (i) a first species of dissolved transition metal ions and additionally metal particles thereof.
- the metal particles comprise one or more than one elemental metal (Me 0 ), preferably (essentially) consist of one or more than one elemental metal (Me 0 ).
- the metal particles of the first spe cies have a particle diameter in a range from 0.1 nm to 500 nm, preferably in a range from 0.5 nm to 200 nm, more preferably in a range from 1.0 nm to 100 nm, most preferably in a range from 3 nm to 50 nm, even most preferably in a range from 5 nm to 15 nm.
- the activation composition is a colloid, preferably a colloidal suspension.
- the activation composi tion is still a clear but colored solution depending on the coloring effect caused by the dis solved ions, primarily of the first species.
- said dissolved transition metal ions of the first species and said metal particles thereof form together a total amount of the metal of the first species.
- a method of the present invention for activating, wherein in the activation composition the metal ions of the first species and the metal particles thereof form a total concentration in a range from 0.05 g/L to 30.0 g/L, based on the total volume of the activation composition and based on an ionic, non-particular form, preferably in a range from 0.07 g/L to 18.0 g/L, more preferably in a range from 0.09 g/L to 12.0 g/L, even more preferably in a range from 0.1 1 g/L to 8.0 g/L, most preferably in a range from 0.15 g/L to 6.0 g/L, even most preferably in a range from 0.2 g/L to 3.0 g/L.
- the transition metal particles of the first species are considered/calculated as dissolved metal ions.
- the method of the present invention (for activating) can be basically carried out with comparatively high concentrations of the first species, it turned out that surprisingly very low concentrations are already sufficient to obtain very efficient and excellent results (see exam ples). This is in particular advantageous in terms of waste-water treatment and is thus cost and ecofriendly.
- Copper and cobalt are cost efficient metals compared to commonly used palladium but achieve sufficient activation on the surface of the non-conduc- tive or carbon-fibres containing substrate.
- concentrations most prefera bly apply to copper and cobalt, most preferably to copper.
- a preferred copper alkyl sul fonate is copper methane sulfonate.
- the most preferred copper source is copper sulfate, most preferably CuSCU * 5 H 2 0.
- the aqueous, palladium-free activation composition comprises (iv) one or more than one second species of dissolved metal ions being different from the first species.
- the second species is substantially free of or does not comprise alkali metals.
- Preferred is a method of the present invention (for activating), wherein the one or more than one second species is substantially free of or does not comprise tin.
- the aqueous, palladium-free activation composition comprises (ii) one or more than one complexing agent.
- the one or more than one complexing agent is suitable to form complexes with the dissolved transition metal ions of at least the first species.
- the one or more than one complexing agent comprises or is an organic complexing agent, preferably a carboxylic acid and/or salts thereof, more preferably a di- or tricarboxylic acid and/or salts thereof, even more preferably a tricarboxylic acid and/or salts thereof, most preferably a hydroxy tricarbox ylic acid and/or salts thereof, even most preferably citric acid, structural isomers, and/or salts thereof.
- a preferred structural isomer is iso-citric acid and salts thereof.
- the one or more than one complexing agent defined above is the only complexing agent in the activation composition.
- Preferred is a method of the present invention (for activating), wherein in the activation com position
- a molar ratio in a range from 1.0 : 0.2 to 1.0 : 100.0, preferably in a range from 1.0 : 0.5 to 1.0 : 50.0, more preferably in a range from 1.0 : 0.85 to 1.0 : 25.0, even more preferably in a range from 1.0 : 0.95 to 1.0 : 15.0, yet even more preferably in a range from 1.0 : 1.0 to 1.0 : 10.0, most preferably in a range from 1.0 : 1.1 to 1.0 : 5.0.
- the one or more than one complexing agent comprises a tricarboxylic acid and/or salts thereof, more preferably a hydroxy tricarboxylic acid and/or salts thereof, most preferably citric acid, structural isomers, and/or salts thereof.
- the aqueous, palladium-free activation composition comprises perma nently or temporarily (iii) one or more than one reducing agent.
- the one or more than one reducing agent is essential for forming the metal particles from the dissolved transition metal ions of at least the first species.
- the dissolved transition metal ions are chemically reduced, continuous or semi-continuous, in order to form said particles.
- said particles are either formed continually or semi-continually, respectively, depending on the presence of the one or more than one reducing agent in the activation composition, which is permanent or temporary.
- the one or more than one reducing agent when the one or more than one reducing agent is present, typically said particles will be formed until said reducing agent is used up or insufficiently present.
- the activation composition In order to prevent precipitating agglomerates during such a time, in the activation composition said oxidation is carried out until no particles are any longer present but rather only dissolved transition metal ions.
- the oxidation is accelerated by adding an oxidizing agent, more preferably a peroxide, most preferably hydrogen peroxide.
- an oxidizing agent more preferably a peroxide, most preferably hydrogen peroxide.
- particles are formed by adding continually or semi-continually the one or more than reducing agent to re-form particles. Afterwards, the method of the present invention (for activating) is resumed.
- the one or more than one reducing agent is suitable for reducing the dis solved transition metal ions of at least the first species.
- the one or more than one reducing agent comprises one or more than one hydrogen atom such that hydrogen is released upon reducing said transition metal ions, which at least partly adsorbs on said activated surface.
- a preferred borohydride comprises an inorganic borohydride and/or an organic borohydride.
- a preferred organic borohydride comprises an alkylaminoborane, most preferably dimethyla- minoborane.
- a preferred inorganic borohydride comprises an alkali borohydride, most prefer ably sodium borohydride.
- most pre ferred is an alkali borohydride, preferably sodium borohydride.
- step (c) of the method of the present invention for activating
- a moderate range preferably from 15°C to 30°C.
- no additional and cost-intensive heating is necessarily required.
- hydrogen is generated.
- the boron-containing reducing agent preferably a borohydride, more preferably an alkali borohydride and/or an alkylaminoborane, most preferably sodium borohydride and/or dimethylaminoborane is the only reducing agent in the activation composition.
- a borohydride in the activation composition as one of the one or more than one reducing agent, typically boric acid and/or salts thereof are formed.
- a method of the present invention for activating is preferred, wherein the one or more than one reducing agent comprises an aldehyde, preferably formaldehyde, glyoxylic acid, salts of glyoxylic acid, or mixtures thereof, most preferably as the only reducing agent. In such a case formation of boric acid is avoided. In some cases a method of the present invention (for activating) is preferred, wherein the one or more than one reducing agent comprises hydrazine, most preferably as the only reducing agent. Also, in such a case formation of boric acid is avoided.
- the activation compo sition comprises the one or more than one reducing agent in a total concentration in a range from 0.2 mmol/L to 500.0 mmol/L, based on the total volume of the activation composition, preferably in a range from 0.4 mmol/L to 350.0 mmol/L, more preferably in a range from 0.6 mmol/L to 250.0 mmol/L, even more preferably in a range from 0.8 mmol/L to 150.0 mmol/L, most preferably in a range from 1.0 mmol/L to 80.0 mmol/L.
- An in particular preferred total concentration is in a range from 0.9 mmol/L to 50.0 mmol/L, very preferably in a range from 1.0 mmol/L to 30.0 mmol/L, most preferably in a range from 1.1 mmol/L to 10.0 mmol/L. Most preferably, this applies to the aforementioned preferred, more preferred, etc. reducing agents; most preferably to a borohydride.
- the one or more than one reducing agent is preferably present (either permanently or temporarily) in such a total concentration that the dissolved transition metal ions of the first species are not quantitatively reduced into the respective particles.
- a method of the present invention (for activating) is preferred, wherein the activation composition does not predominantly exhibit a reductive environment to prevent oxidation of the metal particles.
- oxidation is required and desired.
- a method of the present in vention for activating
- a method of the present invention for activating, wherein in the activation composition - the metal ions of the first species and the metal particles thereof forming together a total concentration based on the total volume of the activation composition and based on an ionic, non-particular form, and
- a molar ratio in a range from 0.3 to 60.0, preferably in a range from 0.5 to 30.0, more preferably in a range from 1.0 to 20.0, even more preferably in a range from 1.5 to 10.0, most preferably in a range from 1.8 to 3.0.
- a method of the present invention for activating is preferred, wherein in the aqueous, palladium-free activation composition the one or more than one reducing agent is permanently present.
- the one or more than one reducing agent is added to the activation composition continually, preferably by a permanent flow of a respec tive liquid containing said one or more than one reducing agent.
- oxidation and reduction are taking place simultaneously over the time during step (c) of the method of the present invention (for activating) is carried out.
- the metal particles are present in a comparatively constant concentration.
- a method of the present invention for activating is preferred, wherein in the aqueous, palladium-free activation composition the one or more than one reducing agent is temporarily present.
- the one or more than one reducing agent is added semi- continuously; e.g. in consecutive portions with time-wise interruptions between each portion. This means that when the one or more than one reducing agent is added fresh particles are formed.
- the oxidation, creating the dissolved transition metal ions is very dominant.
- the metal particles are present in a basically varying concentration.
- a method of the present invention for activating, wherein the one or more than one reducing agent is present in such a way that the equilibrium remains reversible.
- the reversible equilibrium is not only a side reaction or an undesired side reaction.
- the total concentration of the dissolved transition metal ions basically increases as a result of the reversible equilibrium, wherein the total amount of said metal particles decreases.
- This reversible equilibrium is preferably monitored for a better process control. Therefore, preferred is a method of the present invention (for activating), wherein the reversible equilibrium is monitored by UV/VIS inspection.
- said dissolved transition metal ions are monitored at a wave length within a range from 700 nm to 800 nm, preferably within a range from 710 nm to 780 nm, more preferably within a range from 720 nm to 760 nm, most preferably within a range from 730 nm to 750 nm.
- said metal particles are monitored at a wave length within a range from 400 nm to 600 nm, preferably within a range from 450 nm to 550 nm. This allows determining when to add one of the one or more than one reducing agent in order to form, preferably re form, said metal particles in order to increase their total amount.
- a method of the present invention for activating, wherein the one or more than one reducing agent is continually or semi-continually added to the activation composition such that further metal particles are continually or semi-continually, respectively, formed from the dissolved transition metal ions of the first species, preferably added after one or more than one step (c) is carried out.
- step (c) is carried out more than one time, preferably the method, including step (c), is carried out repeatedly.
- metal particles are freshly formed by said reduction. This is possible because said oxidation is allowed and desired, leading, preferably continually but at least semi-continually, to fresh dissolved transition metal ions ready for re-reduction. This is con trary to common approaches, wherein metal particles are formed (and stabilized) before the activation is carried out, which afterwards typically last as long as possible by particle stabili zation until the respective activation composition is unstable and inoperable.
- a reducing agent used for said reduction reacts with the dissolved transition metal ions and leads to a reducing agent degradation product, preferably boric acid and/or salts thereof.
- a reducing agent degradation product preferably boric acid and/or salts thereof.
- a method of the present invention (for activating) is preferred, wherein the method is performed by bleed and feed. In such an approach, a certain volume of the activation composition is removed (e.g. by drag out; thereby removing also degradation products) and replaced by a replacement volume (e.g.
- the replacement volume typically does not comprise boric acid and/or salts thereof, preferably does not comprise the reducing agent degradation product. This is also beneficial for stabilizing the pH to a basically constant pH.
- the activation compo sition comprises boric acid and/or salts thereof in a total concentration of 5 g/L or less, based on the total volume of the activation composition, preferably of 3 g/L or less, more preferably of 2 g/L or less, most preferably of 1.2 g/L or less.
- the one or more than one reducing agent comprises a borohydride and (2) step (c) is carried out more than one time.
- Majority preferably de notes more than 50% of the particles.
- the one or more than one reducing agent is substantially free of or does not com prise hypophosphite ions, preferably is substantially free of or does not comprise a phospho rous-containing reducing agent. Own experiments have shown that in some cases the activa tion with such reducing agents is too weak or even incomplete.
- the activation composition does not additionally require stabilizing compounds. Therefore, preferred is a method of the present invention (for activating), wherein the activation composition is substantially free of or does not comprise a compound prevent ing the oxidation of the metal particles and/or is substantially free of or does not comprise a stabilizer compound to stabilize the metal particles.
- the activation composition is substantially free of or does not comprise a stabilizer compound to stabilize the metal particles by preventing agglomeration of the metal particles.
- the one or more than one reducing agent (temporarily or permanently present in the activation composition) and compounds involved in the oxidation preferably ambient air and/or oxygen gas (i.e.
- the one or more than one reducing agent is rather required in order to form the metal particles, which includes re-forming the particles.
- the activation composition is sub stantially free of or does not comprise in addition to said one or more than one reducing agent and compounds involved in the oxidation a stabilizer compound and/or a compound prevent ing the oxidation of the metal particles.
- a method of the present invention for activating, wherein the one or more than one reducing agent is not present in a total amount to prevent the oxidation, preferably is not present in a total amount to prevent the oxidation after or during one or more than one step (c) is carried out.
- the oxidation most preferably through ambient air, is needed to re-form the dissolved transition metal ions such that no precipitating agglomerates of said metal particles are formed.
- a method of the present invention (for activating) is preferred, wherein the activation compo sition is substantially free of or does not comprise a compound encapsulating fully or partly the metal particles or which fully or partly adsorbs onto the surface of the particles. It is be lieved that some stabilizer compounds are based on such a function. In the context of the present invention this is not desired.
- a method of the present invention (for activating) is preferred, wherein the activa tion composition is substantially free of or does not comprise a compound preventing the equilibrium from being reversible and/or is substantially free of or does not comprise a com pound in order to shift the equilibrium entirely towards the metal particles.
- the one or more than one reducing agent is not considered to be such a compound for the reasons out lined above.
- “metal ions of main group IN” does not include respective boron-containing ions.
- tin ions are very well known to prevent oxidation of for example copper particles in respective palladium-free copper-tin activation compositions, thereby preventing the equilib rium from being reversible.
- Such tin ions typically form a reductive environment, which is by no means desired in the context of the present invention.
- polymers as mentioned above are commonly used as stabilizer compounds in order to stabilize the metal particles.
- polymers are not necessary in the context of the present invention.
- the metal particles are significantly more effective / more active if no such molecules are forming a shell around the particles.
- the activation compo sition is substantially free of or does not comprise a hydroquinone, pyrogallol, and/or resor cinol, preferably is substantially free of or does not comprise a hydroxy benzene.
- hydroxy benzenes are commonly used as anti-oxidizing agents, thereby prevent ing the equilibrium from being reversible, which are not needed in the activation composition.
- the activation composition does not comprise a stabilizing compound and/or a compound preventing the oxidation of the metal particles
- a method of the present invention for activating is preferred, wherein the activation composi tion is substantially free of or does not comprise precipitating agglomerates of said metal par ticles. This is achieved because the oxidation is not suppressed (i.e. is not avoided) but rather the dissolved transition metal ions of at least the first species and the metal particles thereof, respectively, are repeatedly involved in said reduction and said oxidation.
- the preferred oxidizing agent is molecular oxy gen.
- Most preferred is a method of the present invention (for activating), wherein the majority of the dissolved transition metal ions are formed from the majority of the metal particles through oxidation by ambient air and/or oxygen gas.
- a method of the present invention for activating is preferred, wherein the continuous or semi-continuous oxidation is additionally or solely achieved through an oxidiz ing agent, which is not molecular oxygen, more preferably through a peroxide, most preferably hydrogen peroxide.
- an oxidiz ing agent which is not molecular oxygen, more preferably through a peroxide, most preferably hydrogen peroxide.
- this preferably accelerates the oxi dation of the particles if this is required, e.g. if an activation composition must be inactivated and stored for longer times.
- a method of the present invention for activating, wherein the activation composition continually or semi-continually circulates, preferably by shaking, stirring and/or pumping. This is preferred to ensure that the oxidation is equally distributed in the entire activation composition. In other words, this ensures that the metal particles are equally contacted with an oxidizing agent, which facilitates the oxidation.
- one or more than one complexing agent comprising a hydroxy tricarboxylic acid and/or salts thereof, preferably citric acid, structural isomers, and/or salts thereof,
- the activation composition is a colloidal suspension, and - at least of the first species, the dissolved transition metal ions and the metal particles thereof are present in a reversible equilibrium, with the proviso that
- the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
- the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles through oxidation by ambient air,
- step (c) contacting the substrate with said activation composition such that a transition metal or a transition metal alloy is deposited on the surface of said substrate and an activated surface for metallization is obtained, wherein the metal particles are continually or semi-continually formed in situ in the activation composition by said reduction after and/or during one or more than one step (c) is carried out.
- the present invention is also directed to a method for preparing an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization (preferably an activation composition as utilized in the method of the present invention (for activating)), the method comprising the steps
- the present invention is also directed to the use of continuous or semi-continuous reduction of dissolved transition metal ions of a first species in combination with continuous or semi- continuous oxidation of metal particles of the first species in a reversible equilibrium to con tinually or semi-continually form in situ metal particles in an aqueous, palladium-free activation composition.
- the present invention is also directed to an aqueous, palladium-free activation composition for activating a surface of a non-conductive or carbon-fibres containing substrate for metalli zation, the composition comprising
- the metal particles are formed from the dissolved transition metal ions through a continuous or semi-continuous reduction through the one or more than one reducing agent
- the dissolved transition metal ions are formed from the metal particles through continuous or semi-continuous oxidation of said particles, and
- the dissolved transition metal ions and the metal particles thereof, respectively, are repeatedly involved in said reduction and said oxidation such that no pre cipitating agglomerates of said metal particles are formed.
- the aforementioned regarding the method of the present invention (for activating) preferably applies likewise to the aqueous, palladium-free activation composition of the present inven tion, most preferably as aforementioned defined as being preferred.
- the activation composition of the present invention is obtained at and/or has a temperature in a range from 10°C to 90°C, preferably in a range from 14°C to 75°C, more preferably in a range from 16°C to 65°C, most preferably in a range from 18°C to 45°C, even most preferably in a range from 20°C to 32°C.
- a temperature in a range from 18°C to 45°C preferably in a range from 20°C to 32°C, with the proviso that the one or more than one reducing agent is a borohydride, preferably sodium borohydride.
- the activation composition of the present invention is not obtained at and/or has not a temperature above 110°C, preferably above 100°C, more preferably above 95°C. Most preferably the activation composition of the present invention is not obtained at a tem perature above 110°C. This likewise preferably applies to the method of the present invention (for preparing said activation composition) and the method of the present invention (for acti vating).
- step (c) of the method of the present invention for activating
- the substrate is contacted with the aqueous, palladium-free activation composition in order to obtain an activated sur face for metallization by depositing the metal or metal alloy, i.e. depositing a seed or activa tion layer.
- step (c) is a method of the present invention (for activating), wherein in step (c) the con tacting is carried out at a temperature in a range from 10°C to 90°C, preferably in a range from 14°C to 75°C, more preferably in a range from 16°C to 65°C, most preferably in a range from 18°C to 45°C, even most preferably in a range from 20°C to 32°C.
- a temperature in step (c) in a range from 18°C to 45°C, preferably in a range from 20°C to 32°C, and wherein the reduction through the one or more than one reducing agent is a borohydride, preferably sodium borohydride.
- step (c) the con tacting is carried out for a time in a range from 1 minute to 10 minutes, preferably for 2 minutes to 8 minutes, more preferably for 3 minutes to 6 minutes, most preferably for 3.5 minutes to 5 minutes.
- a method of the present invention (for activating) wherein after step (c) a rinsing step is carried out. In such a case a rinsed, activated surface for metallization is obtained.
- the rinsing is carried out with water.
- the present invention furthermore refers to a method for metallizing an activated surface of a non-conductive or carbon-fibres containing substrate, the method comprising the steps
- step (A) of the method of the present invention for metallizing
- the non-conductive or carbon-fibres containing substrate with the activated surface is provided as obtained by the method of the present invention (for activating); for details see text above.
- the aforemen tioned regarding the method of the present invention (for activating), preferably applies to the method of the present invention for metallization, most preferably as described as being preferred.
- step (B) the first metallization layer is a distinct layer deposited on the transition metal or transition metal alloy obtained in step (c) of the method of the present invention (for activating).
- step (B) is a method of the present invention (for metallizing), wherein in step (B) the first metallization solution is essentially free of or does not comprise a reversible equilibrium be tween metal ions and particles thereof; more preferably is essentially free of or does not comprise metal/metal alloy particles, most preferably is essentially free of or does not com prise any particles.
- step (B) the first metallization solution comprises a reducing agent or does not comprise a reducing agent.
- step (B) is carried out at a temperature in a range from 10°C to 95°C, preferably in a range from 15°C to 85°C, more preferably in a range from 20°C to 65°C, even more preferably in a range from 25°C to 55°C, most preferably in a range from 30°C to 45°C.
- step (B) is carried out for 30 seconds to 180 minutes, preferably for 45 seconds to 120 minutes, more prefera bly for 1 minutes to 60 minutes, most preferably for 1.5 minutes to 45 minutes.
- the first metallization solution does not comprise a reducing agent and is an immersion type metal lization solution, preferably comprising one or more than one species of ions selected from the group consisting of palladium ions, platinum ions, silver ions, gold ions, and mercury ions, more preferably comprising palladium ions, most preferably comprising palladium ions in a total concentration in a range from 0.05 mg/L to 20 mg/L.
- step (B) More preferred is a method of the present invention (for metallizing), wherein in step (B) the first metallization solution is an acidic palladium immersion type metallization solution.
- the first metallization solution is an immersion type metallization solution comprising palladium ions in a total concentration in a range from 0.09 mg/L to 10.0 mg/L, based on the total volume of the metallization solution, preferably in a range from 0.1 mg/L to 5.0 mg/L, more preferably in a range from 0.12 mg/L to 3.0 mg/L, even more preferably in a range from 0.15 mg/L to 2.0 mg/L, most preferably in a range from 0.2 mg/L to 1 mg/L, even most preferably in a range from 0.22 mg/L to 0.75 mg/L.
- the metallization solution is acidic.
- the first metallization solution comprises a reducing agent and is an autocatalytic type metallization solution, preferably comprising one or more than one species of transition metal ions, more preferably comprising copper ions and/or nickel ions.
- the first metallization solution is, preferably it is a clear solution without particles.
- a first metallizing solution being an autocatalytic type metallization solution comprising copper ions and a reducing agent such that a first metallization layer comprising copper or a copper alloy is deposited on the activated surface.
- metallizing the activated surface by contacting the activated surface with a first metallizing solution being an immersion type metallization solution comprising palladium ions (preferably as described before) such that a first metallization layer comprising palladium is at least partly deposited on the activated surface, and subsequently
- step (C) the sec ond metallizing solution comprises a reducing agent, preferably comprises a reducing agent and nickel ions.
- step (C) the second metallization layer comprises nickel; preferably is a nickel or a nickel alloy layer.
- step (C) the second metallizing solution comprises a reducing agent, preferably comprises a reducing agent and copper ions.
- step (C) the second metallization layer comprises copper; preferably is a copper or a copper alloy layer.
- step (C) the second metallizing solution comprises a reducing agent, preferably comprises a reducing agent and cobalt ions.
- step (C) the second metallization layer comprises cobalt; preferably is a cobalt or a cobalt alloy layer.
- step (C) the sec ond metallization layer starts deposition within 8 seconds to 30 seconds, preferably within 10 seconds to 25 seconds, most preferably within 12 seconds to 20 seconds.
- the second metallization layer comprises nickel; preferably is a nickel or a nickel alloy layer.
- substrates of either FR4 (Substrate 1 , a resin-containing lami nate, test panels with 5 x 5 cm) or ABS (Substrate 2, a plastic, test panels with 3 cm diam eter) are used.
- each substrate is at least treated with a pre-treatment solution com prising a nitrogen-containing compound, in particular Polyquaternium 6, for 4 minutes at a temperature of approximately 50°C. Afterwards the pre-treated substrates are rinsed with water.
- a pre-treatment solution com prising a nitrogen-containing compound, in particular Polyquaternium 6, for 4 minutes at a temperature of approximately 50°C.
- compositions according to the invention compositions according to the invention, abbreviated in the following as AC, and comparative activation compositions, ab breviated in the following as cAC
- contacting time is carried out for a time sufficient to obtain activated sur faces for subsequent metallization (contacting time).
- the activation compositions according to the present invention comprise citric acid as com- plexing agent.
- the first species is copper.
- the total starting volume of each activation com position is approximately 0.5 L.
- Each activation composition according to the present invention does not comprise (i.e. is totally free of) palladium, a compound intention ally preventing the oxidation of the copper particles, and stabilizer compounds to stabilize the copper particles and to prevent agglomeration.
- the activation compositions basi cally consist of the herewith mentioned ingredients and reaction products thereof.
- Table 1 specific and individual parameters of the first set of examples; concentrations and molar ratios are initial, i.e. prior to a first step (c)
- an aqueous starting solution comprising the dissolved copper ions, the citric acid and optionally the dissolved nickel ions.
- the solution is clear and has a typical blue/bluish colour.
- a boron-containing reducing agent is temporarily present and a part of the dissolved copper ions is immediately reduced such that copper nanoparticles are formed. Typically, not all copper ions are reduced in this initial reduction.
- hydrogen gas is formed. Reduction is basically completed when gas formation ends.
- particle formation particle diameter approximately 10 nm
- the starting solution turns into a colloidal activation composition.
- the colour is dark brown, no precipitating agglomerates are observed.
- the compositions are continually stirred and in continuous contact with ambient air. Thus, oxi dation of the formed particles is not prevented at all, in particular after the reduction is fin ished.
- the respective activation compositions are further stirred and are ready to be utilized for a first activation while the copper particles are still exposed to oxidation.
- step (c) of the method of the present invention (for activating) is carried out for the first time.
- the activation is in each case excellent and sufficient for subsequent metalliza tion.
- AC#1 to AC#3 are stored under stirring for 2 days (initial +2).
- a beginning dis coloration is observed, namely from dark brown to light brown accompanied by an increase of bluish colour. It indicates that the total amount of copper particles decreases and the total concentration of dissolved copper ions increases because of the reversible equilibrium.
- activation is successfully repeated with AC#1 to AC#3 and a second set of sub strates (FR4 and ABS) with very similar backlight results is obtained (for further information regarding backlight test see below).
- cAC#1 showed after 5 days (initial +5) a bluish/greenish colour and precipitating agglomerates.
- cAC#2 appeared blue after initial +5 and was a solu tion without particles. Basically, such an activation composition can be stored and resumed for use after adding another portion of reducing agent. However, in this condition no activa- tion can be obtained with it.
- AC#1 to AC#3 do not additionally need any anti-oxidizing compounds and/or specific stabilizer compounds to prevent agglomeration.
- the activation compositions are kept active over time by maintaining the reversible equilibrium, in particular by even primarily maintaining an oxidizing environment.
- the coverage is evaluated using an industry standard Backlight test, in which the respective substrate is sectioned, so as to allow areas of incomplete coverage to be detected as bright spots when viewed over a strong light source (compare US 2008/0038450 A1 and WO 2013/050332).
- the quality of the coverage is determined by the amount of light that is observed under a conventional optical microscope. The results are given on a scale from D1 to D10, wherein D1 (little, incomplete coverage) means the worst result and D10 (com plete, strong coverage) the best result.
- step (c) of the method of the present invention is carried out after the activation compositions are pre pared.
- the method of the present invention (for metallizing) is carried out with a fist metallization solution in order to obtain a fist metallization layer.
- the first metallization solution is an electroless, autocatalytic copper bath comprising copper ions (approx. 2 g/L Cu 2+ ) and an aldehyde as reducing agent with metallization parameters as follows: pH 11 , 35°C for 20 minutes. After activation, a well adhering first metallization layer of copper is obtained covering entirely the activated surface (no skip plating observed).
- an activation composition e.g. AC#4
- boric acid is present in a total concentration below 0.2 g/L.
- AC#4 is furthermore utilized with the additional modification of intentionally adding boric acid such that the total concentration is 1 g/L (AC#4-1) and 10 g/L (AC#4-10).
- the pH increases to approximately 5.5.
- no difference with respect to activation and metallization is observed.
- AC#4 is repeated with dimethylaminoborane (DMAB) instead of NaBH 4 .
- DMAB dimethylaminoborane
- Activation with AC#8 is carried out with and without pre-treatment equally successful. How ever, higher temperatures are required to obtain an adequate activation compared to exam ples utilizing sodium borohydride.
- activation is tested on FR4 and ABS with an activation composition according to the present invention comprising 0.005 mol/L Cu 2+ , 0.05 mol/L citric acid, and 1.3 mmol/L sodium borohydride. Again, fully activated FR4 and ABS were obtained with excellent backlight test results.
- activation is tested on carbon-fibres containing felt (4.6 mm thickness; approximately 450 g/m 2 area weight, BET surface area 0.4 m 2 /g) with various activation compositions according to the present invention as outlined above in the first and second set of examples. Again, fully nickel-activated felt was obtained in each case. Furthermore, the activated surfaces showed significant catalytic activity in electrolysis form ing hydrogen and oxygen gas.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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CN202080023050.5A CN113614283A (en) | 2019-04-04 | 2020-04-01 | Method for activating a surface of a substrate for metallization of electrically non-conductive or carbon-containing fibers |
KR1020217034886A KR20210143882A (en) | 2019-04-04 | 2020-04-01 | Method for activating the surface of a non-conductive or carbon-fiber containing substrate for metallization |
CA3135816A CA3135816A1 (en) | 2019-04-04 | 2020-04-01 | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
SG11202109533Q SG11202109533QA (en) | 2019-04-04 | 2020-04-01 | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
US17/433,065 US20220154343A1 (en) | 2019-04-04 | 2020-04-01 | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
JP2021558929A JP7455859B2 (en) | 2019-04-04 | 2020-04-01 | Method of activating the surface of a non-conductive or carbon fiber-containing substrate for metallization |
EP20713937.9A EP3947772A1 (en) | 2019-04-04 | 2020-04-01 | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
MX2021012121A MX2021012121A (en) | 2019-04-04 | 2020-04-01 | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization. |
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EP19167282.3 | 2019-04-04 | ||
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US (1) | US20220154343A1 (en) |
EP (1) | EP3947772A1 (en) |
JP (1) | JP7455859B2 (en) |
KR (1) | KR20210143882A (en) |
CN (1) | CN113614283A (en) |
CA (1) | CA3135816A1 (en) |
MX (1) | MX2021012121A (en) |
SG (1) | SG11202109533QA (en) |
TW (1) | TWI764121B (en) |
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WO2022043417A1 (en) | 2020-08-27 | 2022-03-03 | Atotech Deutschland GmbH & Co. KG | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
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- 2020-04-01 JP JP2021558929A patent/JP7455859B2/en active Active
- 2020-04-01 US US17/433,065 patent/US20220154343A1/en active Pending
- 2020-04-01 CA CA3135816A patent/CA3135816A1/en active Pending
- 2020-04-01 KR KR1020217034886A patent/KR20210143882A/en unknown
- 2020-04-01 MX MX2021012121A patent/MX2021012121A/en unknown
- 2020-04-01 WO PCT/EP2020/059313 patent/WO2020201387A1/en unknown
- 2020-04-01 CN CN202080023050.5A patent/CN113614283A/en active Pending
- 2020-04-01 EP EP20713937.9A patent/EP3947772A1/en active Pending
- 2020-04-01 TW TW109111142A patent/TWI764121B/en active
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US20220154343A1 (en) | 2022-05-19 |
KR20210143882A (en) | 2021-11-29 |
TW202041712A (en) | 2020-11-16 |
JP2022527973A (en) | 2022-06-07 |
SG11202109533QA (en) | 2021-10-28 |
MX2021012121A (en) | 2021-11-03 |
JP7455859B2 (en) | 2024-03-26 |
TWI764121B (en) | 2022-05-11 |
CN113614283A (en) | 2021-11-05 |
CA3135816A1 (en) | 2020-10-08 |
EP3947772A1 (en) | 2022-02-09 |
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