EP3940110A1 - Préparations de complexes de métaux précieux - Google Patents

Préparations de complexes de métaux précieux Download PDF

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Publication number
EP3940110A1
EP3940110A1 EP20185479.1A EP20185479A EP3940110A1 EP 3940110 A1 EP3940110 A1 EP 3940110A1 EP 20185479 A EP20185479 A EP 20185479A EP 3940110 A1 EP3940110 A1 EP 3940110A1
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EP
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Prior art keywords
noble metal
layer
substrates
weight
application
Prior art date
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EP20185479.1A
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German (de)
English (en)
Inventor
Robert Sievi
Michael Gock
Richard Walter
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Heraeus Deutschland GmbH and Co KG
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Heraeus Deutschland GmbH and Co KG
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Application filed by Heraeus Deutschland GmbH and Co KG filed Critical Heraeus Deutschland GmbH and Co KG
Priority to EP20185479.1A priority Critical patent/EP3940110A1/fr
Priority to US18/004,581 priority patent/US12435425B2/en
Priority to CN202180042074.XA priority patent/CN115698378A/zh
Priority to PCT/EP2021/060795 priority patent/WO2022012794A1/fr
Priority to JP2022576209A priority patent/JP7645289B2/ja
Priority to TW110118188A priority patent/TWI775446B/zh
Publication of EP3940110A1 publication Critical patent/EP3940110A1/fr
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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 thermal decomposition
    • C23C18/12Chemical 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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical 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 thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208Oxides, e.g. ceramics
    • C23C18/1216Metal oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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 thermal decomposition
    • C23C18/08Chemical 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 thermal decomposition characterised by the deposition of metallic material
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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 thermal decomposition
    • C23C18/12Chemical 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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1295Process of deposition of the inorganic material with after-treatment of the deposited inorganic material

Definitions

  • the present invention relates to preparations of noble metal complexes and the use of the preparations for producing layers comprising noble metal on substrates.
  • WO90/07561 A1 discloses platinum complexes of the formula LM[O(CO)R] 2 , where L is a nitrogen-free cyclic polyolefin ligand, preferably cyclooctadiene (COD) or pentamethylcyclopentadiene, and M is platinum or iridium, and where R is benzyl, aryl or alkyl of four or more Carbon atoms, particularly preferably phenyl. It was an object of the present invention to find preparations which can be used to produce layers comprising noble metal, in particular also on temperature-sensitive substrates.
  • COD cyclooctadiene
  • M platinum or iridium
  • R is benzyl, aryl or alkyl of four or more Carbon atoms, particularly preferably phenyl.
  • diolefinic ligand compound refers to a compound that provides the noble metal complexes with both or two of their olefinic double bonds complexed to a central noble metal atom or complexed to two central noble metals in a bridging manner.
  • n and m generally denote an integer, for example in the range 2 to 5.
  • integer n > 1 is generally in the range 2 to 5; in particular, n is then equal to 2 and it is at the noble metal complexes then to binuclear palladium complexes.
  • integer m generally ranges from 2 to 5; in particular, m is then equal to 2 and the noble metal complexes are then binuclear rhodium or iridium complexes.
  • component (B) is dissolved in component (A). If the optional component (C) is present in a preparation according to the invention, then this component (C) is also preferably present as a solution in component (A).
  • the compositions of the invention are organic solutions, more precisely true, i.e. non-colloidal, organic solutions; the same applies when optional component (C) is present in the preferred form, i.e. dissolved in component (A).
  • the preparations according to the invention contain 30 to 90% by weight of at least one organic solvent (A).
  • the organic solvent or solvents can be selected from a large number of customary organic solvents, since the noble metal complexes have good to unlimited solubility in such organic solvents.
  • the organic solvent or solvents are expediently essentially volatile under the processing conditions of the preparations according to the invention; this applies in particular to the stage after application of a preparation according to the invention to a substrate.
  • the boiling points of the organic solvent or solvents are in the range from 50 to 200°C or higher, for example 50 to 300°C.
  • organic solvents (A) include aliphatics and cycloaliphatics each having 6 to 12 carbon atoms; Halogenated hydrocarbons such as di-, tri- and carbon tetrachloride; aromatics; Araliphatics such as toluene or xylene; alcohols such as ethanol, n-propanol and isopropanol; ether; Glycol ethers such as mono-C1-C4-alkyl glycol ethers and di-C1-C4-alkyl glycol ethers, for example ethylene glycol mono-C1-C4-alkyl ethers, ethylene glycol di-C1-C4-alkyl ethers, diethylene glycol mono-C1-C4-alkyl ethers, diethylene glycol di-C1-C4-alkyl ethers , propylene glycol mono C1-C4 alkyl ether, propylene glycol di-C1-C4 alkyl ether, di-
  • Araliphatics such as toluene or xylene, alcohols such as ethanol, n-propanol and isopropanol and glycol ethers such as mono-C1-C4-alkyl glycol ether and di-C1-C4-alkyl glycol ether, for example ethylene glycol mono-C1-C4-alkyl ether, ethylene glycol di-C1-C4-alkyl ether , diethylene glycol mono-C1-C4-alkyl ether, diethylene glycol di-C1-C4-alkyl ether, propylene glycol mono-C1-C4-alkyl ether, propylene glycol di-C1-C4-alkyl ether, dipropylene glycol mono-C1-C4-alkyl ether and dipropylene glycol di-C1-C4-alkyl ether are included preferred.
  • Constituent (A) or the at least one organic solvent (A) particularly preferably consists of at least one alcohol, specifically at least one of the alcohols mentioned by way of example, and/or of at least one glycol ether, specifically at least one of the glycol ethers mentioned by way of example.
  • At least one alcohol specifically at least one of the alcohols mentioned by way of example
  • glycol ether specifically at least one of the glycol ethers mentioned by way of example.
  • Corresponding mixtures of 30 to 70 parts by weight of alcohol and the part by weight of glycol ether missing from 100 parts by weight are particularly preferred as component (A).
  • the preparations according to the invention contain, as component (B), 10 to 70% by weight of at least one noble metal complex with diolefin and C6-C18 monocarboxylate ligands selected from the group consisting of noble metal complexes of the type [LPd[O(CO)R1] X] n , [LRh[O(CO)R1]] m and [LIr[O(CO)R1]] m , where L is a compound acting as a diolefin ligand, where X is selected from bromide, chloride, iodide and - O (CO)R2, where -O(CO)R1 and -O(CO)R2 are identical or different non-aromatic C6-C18 monocarboxylic acid radicals, each preferably with the exception of a phenylacetic acid radical, and where n is an integer ⁇ 1 and m is an integer number ⁇ 2.
  • the noble metal content of a preparation according to the invention originating from the at least one noble metal complex can be, for example, in the range from 2.5 to 25% by weight.
  • L is a compound functioning as a diolefin ligand at the central palladium atom;
  • X is bromide, chloride, iodide or -O(CO)R2; and -O(CO)R1 and -O(CO)R2 are identical or different non-aromatic C6-C18 monocarboxylic acid residues, each preferably with the exception of a phenylacetic acid residue.
  • n is equal to 1 here.
  • L is a compound functioning as a diolefin ligand;
  • X is bromide, chloride, iodide or -O(CO)R2;
  • n is 2, 3, 4 or 5, preferably 2; and
  • -O(CO)R1 and -O(CO)R2 are identical or different non-aromatic C6-C18 monocarboxylic acid residues, each preferably with the exception of a phenylacetic acid residue.
  • L is a compound functioning as a diolefin ligand; m is 2, 3, 4 or 5, preferably 2; and -O(CO)R1 means one non-aromatic C6-C18 monocarboxylic acid residue, preferably with the exception of a phenylacetic acid residue.
  • Said noble metal complexes can be present in the preparations according to the invention in individualized but also in associated form, ie alone or as a mixture of several different species.
  • palladium complexes can be present in the preparations according to the invention in individualized or in associated form, ie alone or as a mixture of several different species, each of the [LPd[O(CO)R1]X] n type.
  • Rhodium complexes can also be present in the preparations according to the invention in individualized or associated form, ie alone or as a mixture of several different species, each of the [LRh[O(CO)R1]] m type.
  • component (B) may be [LPd[O(CO)R1]X] n and/or [LRh[O(CO)R1]] m and/or [LIr[O( CO)R1]] m ;
  • component (B) may include compounds of only one, two, or all three types disclosed herein, where each type may be present in only one individual form (individualized) or in more than one individual form (socialized).
  • the preparations according to the invention can also comprise platinum compounds of the [LPt[O(CO)R1]X] n type .
  • n has the same meaning as in the palladium complexes of the type [LPd[O(CO)R1]X] n .
  • platinum compounds are disclosed in PCT application serial number PCT/EP2020/068465 .
  • diolefins or compounds of type L capable of functioning as a diolefin ligand examples include hydrocarbons such as COD (1,5-cyclooctadiene), NBD (norbornadiene), COT (cyclooctatetraene) and 1,5-hexadiene, in particular COD and NBD . It is preferably pure hydrocarbons; however, the presence of heteroatoms, for example in the form of functional groups, is also possible.
  • X can mean bromide, chloride, iodide or -O(CO)R2, preferably it means chloride or -O(CO)R2, in particular -O(CO)R2.
  • non-aromatic monocarboxylic acid residues -O(CO)R1 and -O(CO)R2 mean identical or different non-aromatic C6-C18 monocarboxylic acid residues, in each case preferably with the exception of a phenylacetic acid residue.
  • non-aromatic used in this context excludes purely aromatic monocarboxylic acid residues, but not araliphatic monocarboxylic acid residues, the carboxyl function(s) of which is/are attached to aliphatic carbon.
  • -O(CO)R1 and -O(CO)R2 preferably do not mean a phenylacetic acid residue.
  • -O(CO)R1 and -O(CO)R2 are preferably the same non-aromatic C6-C18 monocarboxylic acid residues, but preferably no phenylacetic acid residues.
  • Preferred among the C6-C18 non-aromatic monocarboxylic acid residues are monocarboxylic acid residues having from 8 to 18 carbon atoms, i.e. C8-C18 non-aromatic monocarboxylic acid residues.
  • non-aromatic C6-C18 or the preferred C8-C18 monocarboxylic acids with radicals -O(CO)R1 or -O(CO)R2 include the isomeric hexanoic acids including n-hexanoic acid, the isomeric heptanoic acids including n-heptanoic acid, the isomeric octanoic acids including n-octanoic acid and 2-ethylhexanoic acid, the isomeric nonanoic acids including n-nonanoic acid, and the isomeric decanoic acids including n-decanoic acid, to name just a few examples.
  • radicals R1 and R2 each bonded to a carboxyl group comprise 5 to 17 and 7 to 17 carbon atoms, respectively; Benzyl radicals are preferably excluded in each case.
  • Preferred examples of palladium complexes include [(COD)Pd[O(CO)R1] 2 ] n and [(NBD)Pd[O(CO)R1] 2 ] n where n is 1 or 2, especially 1, and where R1 is a non-aromatic C5-C17 hydrocarbon radical, each preferably with the exception of benzyl.
  • rhodium complexes include [(COD)Rh[O(CO)R1]] m and [(NBD)Rh[O(CO)R1]] m where m is 2 and where R1 is non-aromatic C5-C17 -Hydrocarbon radical, in each case preferably with the exception of benzyl.
  • iridium complexes include [(COD)Ir[O(CO)R1]] m and [(NBD)Ir[O(CO)R1]] m where m is 2 and where R1 is non-aromatic C5-C17 -Hydrocarbon radical, in each case preferably with the exception of benzyl.
  • the noble metal complexes can be prepared in a simple way by ligand exchange, in particular without using carboxylic acid salts of silver.
  • the manufacturing process includes mixing or suspending or emulsifying a two-phase system.
  • One phase comprises a starting material of the type LPdX 2 or [LRhX] 2 or [LIrX] 2 in each case with X selected from bromide, chloride and iodide, preferably chloride, either as such or preferably in the form of an at least essentially water-immiscible organic solution such an educt.
  • Examples of at least essentially water-immiscible organic solvents suitable for producing such an organic solution include aromatics and chlorinated hydrocarbons such as toluene, xylene, dichloromethane, trichloromethane and carbon tetrachloride, as well as oxygen-containing solvents, for example corresponding water-immiscible ketones, esters and ethers.
  • the other phase comprises, for example, an aqueous solution of alkali metal salt (particularly sodium or potassium salt) and/or magnesium salt of a C6-C18 monocarboxylic acid of the R1COOH type and optionally also of the R2COOH type.
  • the choice of the type of monocarboxylic acid salt or salts depends on the type of noble metal complex to be produced or the group of noble metal complexes to be produced.
  • the two phases are thoroughly mixed to form a suspension or emulsion, for example by shaking and/or stirring.
  • the mixing is carried out, for example, for a period of 0.5 to 24 hours, for example at a temperature in the range from 20 to 50.degree.
  • the ligand exchange takes place, with the noble metal complex or complexes formed dissolving in the organic phase, while the alkali metal salt or MgX 2 salt also formed dissolves in the aqueous phase.
  • the organic and aqueous phases are separated from one another.
  • the noble metal complex or complexes formed can be obtained from the organic phase and, if appropriate, subsequently purified using customary methods.
  • (COD)Pd[O(CO)CH(C 2 H 5 )C 4 H 9 ] 2 can be prepared by co-emulsifying a solution of (COD)PdCl 2 in dichloromethane with an aqueous Solution of sodium 2-ethylhexanoate are prepared. After the end of the emulsification, this can be done by ligand exchange
  • the solution containing common salt formed is separated from the dichloromethane phase and the (COD)Pd[O(CO)CH(C 2 H 5 )C 4 H 9 ] 2 is isolated from the latter and, if appropriate, purified by customary purification processes.
  • the palladium complex (COD)Pd[O(CO)CH(C 2 H 5 )C 4 H 9 ]Cl can also be prepared analogously, for example with a correspondingly selected stoichiometry.
  • an important property in addition to the aforementioned solubility in customary organic solvents, is the comparatively low decomposition temperature of the noble metal complex(es) of component (B), for example from as little as 150.degree. C. to 250.degree. C., often not higher than 200.degree.
  • This combination of properties makes it possible to use such noble metal complexes as component (B) of the preparations according to the invention for the production of layers comprising noble metal on substrates;
  • the preparation according to the invention represents a coating composition (coating composition), i.e. it is then prepared and usable as a coating composition.
  • the preparations according to the invention contain 0 to 10% by weight, preferably 0 to 3% by weight, of at least one additive (C).
  • the preparations according to the invention can therefore be additive-free or contain up to 10% by weight of at least one additive.
  • additives include wetting additives, rheology additives, defoamers, deaerators, surface tension additives, and odorants.
  • Formulations according to the invention can be prepared by simply mixing ingredients (A), (B) and, if desired, (C).
  • ingredients (A), (B) and, if desired, (C) The person skilled in the art selects the quantitative ratio of the components adapted to the respective intended use and/or the application method to be used.
  • the preparations according to the invention can be used to produce layers comprising noble metal on substrates, in particular also on temperature-sensitive substrates.
  • the preparations according to the invention can first be used to produce covering layers (coatings), which can then be subjected to thermal decomposition.
  • essentially metallic palladium is formed in the form of a layer during thermal decomposition even in the presence of air as the surrounding atmosphere; during thermal decomposition when working with preparations according to the invention Based on rhodium complexes of the type [LRh[O(CO)R1]] n or based on iridium complexes of the type [LIr[O(CO)R1]] n, on the other hand, when air is present as the ambient atmosphere, essentially corresponding noble metal oxide layers or even of corresponding metallic noble metal free noble metal oxide layers.
  • layer comprising precious metal used herein as a layer comprising or consisting essentially or even only of metallic palladium, as a layer comprising or consisting essentially or even only of rhodium oxide or as a layer comprising or consisting essentially or even only of iridium oxide existing layer, briefly stated as a layer comprising or consisting of metallic palladium, rhodium oxide or iridium oxide.
  • palladium layers obtainable according to the invention on substrates show the properties to be expected by a person skilled in the art
  • layers essentially comprising rhodium oxide or essentially iridium oxide or substrate surfaces equipped therewith which can be obtained according to the invention on substrates can have interesting electrical properties.
  • the substrates to be provided with the coating layer in step (1) may be substrates comprising various materials.
  • the substrates can only include one or more materials. Examples of materials include, but are not limited to, glass; carbide substrates such as titanium carbide, molybdenum carbide, tungsten carbide, silicon carbide; nitride substrates such as aluminum nitride, titanium nitride, silicon nitride; boride substrates such as titanium boride, zirconium boride; Ceramic substrates, including those based on oxidic ceramics and those customary as catalyst supports in heterogeneous catalysts; semiconductor substrates such as silicon substrates; Metal; Plastic; modified or unmodified polymers of natural origin; carbon substrates; Wood; cardboard and paper.
  • the substrates can be provided with the coating layer on inner and/or outer surfaces and/or on inner and/or outer surface portions.
  • a first application method is dipping.
  • the substrate to be provided with the coating layer or the layer finally to be provided with the precious metal is immersed in and removed from the preparation according to the invention.
  • the proportion of the Constituent (A) in dipping ranges from 30 to 90% by weight of the composition of the invention and that of constituent (B) ranges from 10 to 70% by weight.
  • a second application method is spray application.
  • the substrate to be provided with the coating layer or the layer finally comprising the noble metal is spray-coated with the preparation according to the invention using a conventional spray-coating tool.
  • spray coating tools are pneumatic spray guns, airless spray guns, rotary atomizers or the like.
  • the proportion of constituent (A) is preferably in the range from 50 to 90% by weight of the preparation according to the invention and that of constituent (B) in the range from 10 to 50% by weight.
  • a third application method is printing.
  • the substrate to be provided with the coating layer or the final layer comprising the precious metal is printed with the preparation according to the invention.
  • a preferred printing method is inkjet printing; the preparation according to the invention represents a coating material in the form of an ink.
  • Another preferred printing process is screen printing.
  • the proportion of component (A) during printing is preferably in the range from 50 to 90% by weight of the preparation according to the invention and that of component (B) in the range from 10 to 50% by weight.
  • a fourth application method is application using an application tool impregnated with the preparation according to the invention, for example a brush, a brush, a felt or a cloth.
  • the preparation according to the invention is transferred from the application tool to the substrate to be provided with the coating layer or the layer finally comprising the precious metal.
  • the proportion of component (A) is preferably in the range from 30 to 90% by weight of the preparation according to the invention and that of component (B) in the range from 10 to 70% by weight.
  • the coating layer comprising at least one component (B) applied from a preparation according to the invention can first be dried and partially or completely freed from the organic solvent (A) before it or the dried residue is subjected to thermal decomposition to form the layer comprising noble metal .
  • thermal decomposition taking place thermal treatment includes heating to an object temperature above the decomposition temperature of at least a noble metal complex (B). If several different noble metal complexes (B) are present, the person skilled in the art will choose the object temperature above the decomposition temperature of the noble metal complex of type (B) with the highest decomposition temperature.
  • the object is heated briefly to an object temperature above the decomposition temperature, for example for a period of 1 minute to 30 minutes to an object temperature in the range from >150°C to 200°C or from >150 to 250°C or higher, for example up to 1000°C.
  • the heating can take place in particular in an oven and/or by infrared radiation.
  • an object temperature slightly above the relevant decomposition temperature is chosen.
  • heating, more precisely maintaining the object temperature takes no more than 15 minutes.
  • Palladium layers obtainable according to the invention are distinguished by a high metallic luster comparable to a mirror, provided that substrates with smooth, not too rough surfaces are used; the palladium layers are homogeneous in the sense of a smooth, non-granular outer surface.
  • the thickness of layers comprising noble metal obtainable according to the invention can be for example in the range from 50 nm to 5 ⁇ m and the layers comprising noble metal can have a planar nature with or without desired interruptions within the area or have a desired pattern or design.
  • the layers comprising noble metal can even be produced on temperature-sensitive substrates, ie for example on substrates which are not temperature-stable above 200° C.; for example, it may be act temperature-sensitive polymer substrates, such as those based on polyolefin or polyester.
  • Example 1 (equipping a polyimide film with a palladium layer):
  • Example 2 (equipping a polyimide film with a patterned palladium layer):
  • a Kapton ® film was dpi using an inkjet printer with a resolution of 1270 printed in a meander design with the solution from Example. 1
  • the film printed in this way was heated to an object temperature of 200° C. in a laboratory oven and held at this temperature for 5 minutes.
  • a shiny, electrically conductive layer of palladium had formed on the foil in the form of the meander design with a width of the conductor tracks of 2.5 mm.
  • Example 3 (equipping a polyimide film with a palladium layer):
  • Example 1 was repeated completely analogously with the only difference that (NBD)PdCl 2 was used instead of (COD)PdCl 2 , so that as a result of the synthesis a yellow residue of (NBD)Pd[O(CO)CH(C 2 H 5 )C 4 H 9 ] 2 and finally one with a palladium layer provided polyimide film corresponding to the coated film obtained in Example 1 was obtained.
  • Example 4 (equipping a polyimide film with a patterned palladium layer):
  • Example 2 was repeated completely analogously with the only difference that (NBD)PdCl 2 was used instead of (COD)PdCl 2 , so that as a result of the synthesis a yellow residue of (NBD)Pd[O(CO)CH(C 2 H 5 )C 4 H 9 ] 2 and finally a palladium-patterned polyimide film corresponding to the palladium-patterned film obtained in Example 2 was obtained.
  • Example 5 (equipping a polyimide film with a rhodium oxide layer):
  • Example 6 (equipping a polyimide film with a patterned rhodium oxide layer):
  • a Kapton ® film was dpi using an inkjet printer with a resolution of 1270 printed in a meandering design with the solution from Example 5.
  • FIG. The film printed in this way was heated to an object temperature of 250° C. in a laboratory oven and held at this temperature for 5 minutes.
  • a matt layer of essentially rhodium oxide had formed on the foil in the form of the meander design with a width of the conductor tracks of 2.5 mm.
  • Example 7 (equipping a polyimide film with a rhodium oxide layer):
  • Example 5 was repeated completely analogously with the only difference that [(NBD)RhCl] 2 was used instead of [(COD)RhCl] 2 , so that as a result of the synthesis a yellow residue of [(NBD)Rh[O(CO )CH(C 2 H 5 )C 4 H 9 ]] m and finally a polyimide film provided with a matt layer of essentially rhodium oxide, which corresponded to the coated film obtained in example 5, was obtained.
  • Example 8 (equipping a polyimide film with a patterned rhodium oxide layer):
  • Example 6 was repeated completely analogously with the only difference that [(NBD)RhCl] 2 was used instead of [(COD)RhCl] 2 , so that as a result of the synthesis a yellow residue of [(NBD)Rh[O(CO )CH(C 2 H 5 )C 4 H 9 ]] m and finally a substantially rhodium oxide patterned polyimide film corresponding to the substantially rhodium oxide patterned film obtained in Example 6 was obtained.
  • Example 9 (equipping a polyimide film with an iridium oxide layer):
  • Example 10 (Equipping a polyimide film with a patterned iridium oxide layer):
  • a Kapton ® film was dpi using an inkjet printer with a resolution of 1270 printed in a meander design with the solution from Example. 9
  • the film printed in this way was heated to an object temperature of 250° C. in a laboratory oven and held at this temperature for 5 minutes.
  • On the film had a matte layer of essentially Iridium oxide formed in the shape of the meander design with a 2.5 mm width of the conductor tracks.

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EP20185479.1A 2020-07-13 2020-07-13 Préparations de complexes de métaux précieux Pending EP3940110A1 (fr)

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EP20185479.1A EP3940110A1 (fr) 2020-07-13 2020-07-13 Préparations de complexes de métaux précieux
US18/004,581 US12435425B2 (en) 2020-07-13 2021-04-26 Preparations of noble metal complexes
CN202180042074.XA CN115698378A (zh) 2020-07-13 2021-04-26 贵金属络合物的制剂
PCT/EP2021/060795 WO2022012794A1 (fr) 2020-07-13 2021-04-26 Préparations de complexes de métaux précieux
JP2022576209A JP7645289B2 (ja) 2020-07-13 2021-04-26 貴金属錯体の調製物
TW110118188A TWI775446B (zh) 2020-07-13 2021-05-20 貴金屬錯合物之配製物

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022111991A1 (de) 2022-05-12 2023-11-16 Heraeus Deutschland GmbH & Co. KG Nasschemische Edelmetallbeschichtung
US12133733B2 (en) 2020-11-10 2024-11-05 Heraeus Deutschland GmbH & Co. KG Production method for noble metal electrodes
DE102023135112A1 (de) * 2023-12-14 2025-06-18 Heraeus Medevio GmbH & Co. KG Flexible Leiterplatte und Verfahren zum Herstellen davon

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990007561A1 (fr) 1988-12-28 1990-07-12 Fuel Tech, Inc. Procede de reduction des emissions provenant de moteurs a combustion interne ou d'augmentation de l'energie utilisable du carburant alimentant des moteurs a combustion interne
US5763633A (en) * 1996-05-29 1998-06-09 Micron Technology, Inc. Metal carboxylate complexes for formation of metal-containing films on semiconductor devices
WO2012167198A2 (fr) * 2011-06-03 2012-12-06 Emory University Compositions de catalyseur dirhodium et procédés de synthèse s'y rapportant
US20130202795A1 (en) * 2012-02-02 2013-08-08 Xerox Corporation Composition of palladium unsaturated carboxylate and palladium nanoparticles
DE102014222996A1 (de) * 2014-11-11 2016-05-12 Heraeus Deutschland GmbH & Co. KG Gold-Zusammensetzung für Dekor mit ausgewählter Metallzusammensetzung sowie Verfahren zur Herstellung derselben

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08277473A (ja) * 1995-04-07 1996-10-22 Mitsubishi Materials Corp Ir膜又は酸化Ir膜形成用組成物、並びに、この組成物より形成したIr膜、酸化Ir膜、Ir膜パターン及び酸化Ir膜パターン
JP3384228B2 (ja) * 1996-03-01 2003-03-10 三菱マテリアル株式会社 金属錯体及び金属薄膜形成方法
JP3917037B2 (ja) * 2002-07-29 2007-05-23 ナミックス株式会社 外部電極及びそれを備えた電子部品
JP6640098B2 (ja) * 2014-02-05 2020-02-05 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングMerck Patent GmbH 金属錯体
US11319332B2 (en) * 2017-12-20 2022-05-03 Basf Se Process for the generation of metal-containing films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990007561A1 (fr) 1988-12-28 1990-07-12 Fuel Tech, Inc. Procede de reduction des emissions provenant de moteurs a combustion interne ou d'augmentation de l'energie utilisable du carburant alimentant des moteurs a combustion interne
US5763633A (en) * 1996-05-29 1998-06-09 Micron Technology, Inc. Metal carboxylate complexes for formation of metal-containing films on semiconductor devices
WO2012167198A2 (fr) * 2011-06-03 2012-12-06 Emory University Compositions de catalyseur dirhodium et procédés de synthèse s'y rapportant
US20130202795A1 (en) * 2012-02-02 2013-08-08 Xerox Corporation Composition of palladium unsaturated carboxylate and palladium nanoparticles
DE102014222996A1 (de) * 2014-11-11 2016-05-12 Heraeus Deutschland GmbH & Co. KG Gold-Zusammensetzung für Dekor mit ausgewählter Metallzusammensetzung sowie Verfahren zur Herstellung derselben

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12133733B2 (en) 2020-11-10 2024-11-05 Heraeus Deutschland GmbH & Co. KG Production method for noble metal electrodes
DE102022111991A1 (de) 2022-05-12 2023-11-16 Heraeus Deutschland GmbH & Co. KG Nasschemische Edelmetallbeschichtung
DE102023135112A1 (de) * 2023-12-14 2025-06-18 Heraeus Medevio GmbH & Co. KG Flexible Leiterplatte und Verfahren zum Herstellen davon

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CN115698378A (zh) 2023-02-03
US12435425B2 (en) 2025-10-07
TW202206443A (zh) 2022-02-16
JP7645289B2 (ja) 2025-03-13
WO2022012794A1 (fr) 2022-01-20
TWI775446B (zh) 2022-08-21
US20230243038A1 (en) 2023-08-03
JP2023532192A (ja) 2023-07-27

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