WO2019224286A1 - Revêtements anti-empreintes digitales - Google Patents

Revêtements anti-empreintes digitales Download PDF

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Publication number
WO2019224286A1
WO2019224286A1 PCT/EP2019/063294 EP2019063294W WO2019224286A1 WO 2019224286 A1 WO2019224286 A1 WO 2019224286A1 EP 2019063294 W EP2019063294 W EP 2019063294W WO 2019224286 A1 WO2019224286 A1 WO 2019224286A1
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WIPO (PCT)
Prior art keywords
silicone
compound
coating mixture
metal substrate
coating
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PCT/EP2019/063294
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English (en)
Inventor
Mutlu-Iskender MUGLALI
Peter Kühlkamp
Philipp Wachter
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Atotech Deutschland Gmbh
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Filing date
Publication date
Application filed by Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Priority to JP2020564436A priority Critical patent/JP7326342B2/ja
Priority to EP19725185.3A priority patent/EP3802914A1/fr
Priority to CN201980032987.6A priority patent/CN112189061A/zh
Publication of WO2019224286A1 publication Critical patent/WO2019224286A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—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 thermal decomposition
    • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—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 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
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • 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
    • C23C18/02—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 thermal decomposition
    • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/02—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 thermal decomposition
    • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the present invention relates to a novel method for coating a metal substrate, in particular a chromium substrate, with an anti-fingerprint coating by coating the metal substrate using a silicone coating mixture and to the use of said silicone coating mixture for coating said metal substrate.
  • Chromium and other metals have found extensive use as decorative materials in a plurality of applications, for example for automotive parts both in the inside of vehicle interior and for parts mounted on the exterior of a car body, for white goods such as refrigerators, stoves, washing machines and dishwashers, for consumer electronics such as mobile phones, in sanitary appliances, as well as for classical chromium layers included in anti-corrosion coatings used for decorative equipment for example. All these surfaces may adversely be affected by dirt adhering to them so that their appearance will be impaired, in particular fatty or greasy contaminants. The latter type of stains cannot be removed easily using hydrous cleaning material and would therefore resistantly affect the appearance of a metal coated article. Fingerprints are frequently applied to decorative surfaces as a consequence of their manual handling during everyday use. Due to the inherent fat material included in human exudation, such soiling of the decorative surfaces is frequently experienced in decoratively designed parts.
  • the surfaces of chromium coatings which are deposited from Cr(lll) containing plating compositions are more sensitive to such impairment due to fingerprints than the surfaces of chromium coatings which are deposited using Cr(VI) containing plating compositions.
  • This different behavior may be due to the fact that the chromium surfaces produced using Cr(lll) containing plating compositions are darker than the chromium surfaces produced using Cr(VI) containing plating compositions.
  • This problem is even more serious on surfaces of chromium deposits which are produced by using chloride containing Cr(lll) containing plating compositions. In this latter case, fingerprints will be the most sensitive towards impairment as these surfaces are relatively dark.
  • US 2008/0131706 A1 teaches the use of polysilazanes as permanent coatings on metal surfaces, stainless steel, aluminium or chromium-plated surfaces for example, for the prevention of the susceptibility to fingerprints.
  • DE 10 2005 018 740 A1 teaches a hydrophobic protective coating for metal surfaces which is free of fluorine in order to prevent the formation of fingerprints.
  • the protective coating consists of hydrolysis and condensation products of (a) 50 to 65 % by weight of tetraalkoxy compounds of silicon, titanium, zirconium; (b) 20 to 30 % by weight of methyl trialkoxy silane; (c) 10 to 20 % by weight of alkyl trialkoxy silane comprising C 12 to C 18 alkyl; (d) 2 to 5 % by weight of polyalkyleneoxide trialkoxy silane.
  • US 6,251 ,989 B1 teaches an oligomerized polyorganosiloxane co-condensate which may be obtained, in part, by mixing a water-soluble amino-functional organosilane represented with at least one of the following: a fluoro-functional organosilane and one of various types of organosilanes.
  • US 8,889,812 B2 teaches an aqueous composition based on tris-silylated amino-functional silicon compounds, which is substantially free of organic solvents and which substantially does not release any alcohol even during the cross-linking process.
  • alkyl refers to a saturated linear or branched-chain mono- or divalent hydrocarbon radical of one to twelve carbon atoms (CrC 12 ), preferably of one to six carbon atoms (Ci -Ce), wherein one or more hydrogen atoms of the alkyl radical may be optionally substituted independently by a respective number of the substituents described below.
  • alkyl groups include, but are not limited to, methyl (-CH 3 ), ethyl (-CH 2 CH 3 ), 1 - propyl (-CH 2 CH 2 CH 3 ), 2-propyl (-CH(CH 3 ) 2 ),1 -butyl (-CH 2 CH 2 CH 2 CH 3 ), 2-methyl- 1 -propyl (-CH 2 CH(CH 3 ) 2 ), 2-butyl (-CH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propyl (-C(CH 3 ) 3 ), 1 -pentyl
  • Alkyl also includes, but is not limited to, methylene (-CH 2 -), ethylene
  • fluoroalkyl refers to a saturated linear or branched-chain monovalent hydrocarbon radical of one to twelve carbon atoms (CrC 24 ), preferably of one to six carbon atoms (CrC 12 ), wherein one or more hydrogen atoms of the alkyl radical of fluoroalkyl is substituted by a respective number of fluorine atoms. If all hydrogen atoms of the alkyl radical are substituted by fluorine, the fluoroalkyl is perfluoroalkyl. For the rest, the same definitions and examples as given above for the term“alkyl” apply mutatis mutandis to fluoroalkyl.
  • fluoroalkylalkyl refers to fluoroalkyl which has a perfluoroalkyl moiety and an alkyl moiety, wherein the perfluoroalkyl moiety may, in a first alternative, form a monovalent radical and the alkyl moiety may form a bivalent moiety, i.e., it may have the chemical formula C n F2 n-i -C n H 2n - ⁇
  • the perfluoroalkylalkyl moiety may form a bivalent perfluoroalkyl moiety and a monovalent alkyl moiety, i.e., it may have the chemical formula C n H2 n-i -C n F 2n -.
  • Alkyl may be substituted, wherein one or more hydrogen atoms thereof may be optionally substituted independently by any radical group like aryl, heteroaryl, OR, NR’R”, COOR, CONR’R”, wherein R, R’, and R” are, independently, selected from hydrogen, alkyl, aryl and heteroaryl.
  • Heteroaryl is a monovalent radical comprising an aromatic ring system which includes at least one of N, S and O, such as pyridyl, pyrryl, thiophenyl, furanyl, and the like.
  • Aryl means a mono- or divalent aromatic hydrocarbon radical of 6-20 carbon atoms (C 6 -C 2 o) derived by the removal of one or two hydrogen atoms, resp., from one or two carbon atoms, resp., of a parent aromatic ring system.
  • Aryl also includes bicyclic radicals comprising an aromatic ring fused to an aromatic carbocyclic ring.
  • Typical aryl groups include, but are not limited to, radicals derived from benzene (phenyl), substituted benzenes, naphthalene and the like.
  • One or more hydrogen atoms of aryl may be optionally substituted independently by a respective number of substituents described herein below.
  • aryl one or more hydrogen atoms thereof may be optionally substituted independently by a respective number of substituents, wherein at least one hydrogen atom of the aryl moiety is substituted by any radical group like Hal, alkyl, aryl, heteroaryl, OR, NR’R”, COOR, CONR’R”, wherein R, R’ and R” are independently selected from hydrogen, alkyl, aryl and heteroaryl.
  • halogen or“Hal” as used herein refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • siloxane refers to silicon compounds which contain [-0-Si(0H)(R)]- and/or [-0-Si(R)(R’)]- moieties, wherein R, R’ mean H, alkyl, aryl, including substituted alkyl and aryl and which typically form a [-O-Si]- backbone. In these compounds terminal moieties may be different from the definitions for R, R’.
  • a metal substrate such as a chromium, nickel or stainless steel substrate, in particular a chromium substrate, with an anti-fingerprint coating, the method comprising:
  • oligo is used e.g. in oligo(aminoalkyl)-fluoroakyl silicones, oligo is understood as synonym of a small number of units to be read as 2-8, preferably 2-6 more preferably 2 or 3; or to be read as dimer, trimer, tetramer ... octamer.
  • Fluoroalkyl in the at least one first silicone compound is preferably perfluoroalkylalkyl and more preferably has the chemical formula C n F 2n _
  • the silicone coating mixture may contain one mono- or oligo(aminoalkyl)-fluoroalkyl silicone or a plurality of mono- or oligo(aminoalkyl)-fluoroalkyl silicones, wherein these silicones may differ from each other by at least one of the chain length of the mono- or oligo(aminoalkyl) moiety, the meaning of aminoalkyl, comprising the meaning of R’ in -N(R’)- and the meaning of fluoroalkyl for example.
  • the silicone coating mixture may contain one aminoalkyl silicone or a plurality of aminoalkyl silicones, wherein these silicones may differ from each other by at least one of the chain length of the silicone chain and the meaning of aminoalkyl, comprising the meaning of R’ and R” in R’R”N-alkyl for example.
  • silicone coating mixture for coating the metal substrate with the anti-fingerprint coating.
  • Said silicone coating mixture comprises: (i) at least one first silicone compound selected from the group consisting of mono- or oligo(aminoalkyl)-fluoroalkyl silicones; (ii) at least one second silicone compound selected from the group consisting of aminoalkyl silicones; (iii) at least one acidifier; and (iv) water.
  • the metal substrate By coating the metal substrate with the anti-fingerprint coating, a superior finish of the metal surface is achieved which is very much resistant against soiling with fatty or greasy material, such as against fingerprint formation, and wherein any fingerprint soils are easily removed mechanically from the surface. Such removal may be performed using a microfiber cloth, for example.
  • the anti-fingerprint coating ensures retention of the original appearance of the metal surface as prepared because it does not change the color tone or surface morphology thereof.
  • treatment of the metal surface according to the invention with the silicone coating mixture is very easy and does not afford lengthy and laborious as well as extensive energy consuming processes, but instead makes possible quick treatment at low processing temperature.
  • the chemicals used are are water soluble, they will not require any organic solvents as solubilizer.
  • the compounds contained in the silicone coating mixture adsorb to the metal substrate and, during the curing step, undergo a chemical reaction to form a very thin, non-visible and mechanically resistant top-coat thereon.
  • the method of the invention is a sol-gel process that is based on adsorption of silicon containing compounds from a mixture of different organo-functional silicon compounds and optionally at least one polyether siloxane copolymer surfactant in a solution. Due to the top coat, surface energy of the substrate is lowered relative to the non-coated state. Therefore, it is possible to monitor formation of the coating by contact-angle measurements.
  • the silicone coating mixture is a liquid, more preferably an aqueous liquid and most preferably an aqueous solution or aqueous sol (colloid solution).
  • the metal substrate is produced in a conventional manner.
  • the metal substrate may be in the form of any work piece made of any material and coated with a deposit of any metal.
  • the work piece material may preferably be a plastics, metal, glass, ceramics material or any other material.
  • the work piece may be provided as any automotive part or sanitary part or any part for building equipment or part for electronic or audiovisual equipment or any other part exhibiting a decorative property.
  • the metal deposit is preferably a nickel coating or stainless steel coating or, most preferably, a chromium coating.
  • the metal substrate is a chromium substrate, more preferably a chromium metal layer forming the substrate which is deposited onto the work piece.
  • the chromium substrate is produced by depositing a chromium metal layer on the work piece.
  • an undercoat is first produced on the work piece prior to depositing the chromium metal layer thereon.
  • Such undercoat may consist of a plurality of metal layers in order to yield optimum decorative (leveling, brightening) and functional (anti-corrosion) properties of the overall metal coating.
  • the undercoat may for example consist of a base copper metal layer and one or a plurality of nickel metal layers which are arranged directly underneath the chromium metal layer.
  • These metal layers are in general electroplated by using appropriate metal plating compositions. Such sandwich metal coating and the deposition methods thereof are well-known to those in the pertinent technical field.
  • Depositing the chromium metal layer comprises providing the work piece and an electroplating liquid which contains at least one chromium plating species, more preferably a Cr(lll) plating species, and electroplating the chromium metal layer onto the work piece by using the electroplating liquid containing the at least one chromium plating species, more specifically containing the Cr(lll) plating species.
  • the chromium coating can be produced in a conventional manner.
  • electroplating is performed by using an electroplating liquid (composition) which comprises Cr(lll) species, such as chromium(lll) chloride, chromium(lll) sulfate or basic chromium(lll) sulfate.
  • electroplating liquids typically furthermore contain one or more buffering agents as boric acid and carbonic acid, conductivity salts as ammonia sulfates, sodium sulfates, potassium sulfates and halides, one or more complexing agents as carbonic acid and amino acids, and a wetting agent as sulfosuccinates.
  • dark chromium metal layers are desired darkening agents can be added.
  • Such liquids are commercially available, and a person skilled in the art is well-acquainted in using such liquids for producing chromium coatings on the work piece to be electroplated.
  • the Cr(lll) plating species containing liquid is free of chloride species.
  • the at least one first silicone compound selected from the group consisting of mono- or oligo(aminoalkyl)-fluoroalkyl silicones is a water soluble statistical copolymer of an mono- or oligo(aminoalkyl) silicone and a (fluoroalkyl)alkylsilicone.
  • the at least one first silicone compound is derived from an aqueous co-condensation of at least two monomeric building blocks selected from the group consisting an mono- or oligoaminoalkyltrihydroxysilane compound and a fluoroalkylalkyltrihydroxysilane compound, wherein the aminoalkyltrihydroxysilane compound has the general chemical formula (I):
  • x is 1 -8, preferably 1 -6, more preferably 1 -4
  • y is 1 -6, preferably 1 -4, more preferably 1 -2
  • z is 0-8, preferably 0-6, more preferably 0-4, most preferably 1 or 2, and wherein the fluoroalkylalkyltrihydroxysilane compound has the general formula (II):
  • a is 1 -8, preferably 1 -6, more preferably 1 -4
  • b is 0-20, preferably 0-10, more preferably 0-5, most preferably 2-5.
  • Molar relation of the aminoalkyltrihydroxysilane compound to fluoroalkylalkyltrihydroxysilane compound ranges preferably from 1 : 10 to 10: 1.
  • the first silicone compound derived from an aqueous co-condensation wherein the aminoalkyltrihydroxysilane compound is (HO) 3 Si-(CH 2 ) 3 -[NH(CH 2 ) 2 ] 2 -NH 2 and the fluoroalkylalkyltrihydroxysilane compound is (HO) 3 Si-(CH 2 ) 2 -(CF 2 ) 5 CF 3 .
  • the average of the molecular weight of the at least one first silicone compound is from 200 to 3,000 g/mole, more preferably from 300 to 2,000 g/mole, most preferably from 400 to 1 ,000 g/mole as determined by gel permeation chromatography against polyethylene oxide standards.
  • Dynasylan® SIVO 1 12 (CAS No. 1222158-90-8) and Dynasylan® F 8815 available from Evonik, WASF-151 1 available from Gelest Inc., may be used as one of the at least one first silicone compound.
  • a method of producing these compounds above is described e.g. in US 8,889,812 B2, US 6,251 ,989 B1 and EP1 101787B1 , which are hereby incorporated. This compound has proven to be most responsible for providing low surface energy to the metal substrate.
  • the at least one second silicone compound is a water soluble polymeric aminoalkylsilicone compound which can be derived from aqueous condensation of at least one monomeric building block selected from the group consisting of an aminoalkyltrihydroxysilane compound, wherein the aminoalkyltrihydroxysilane compound has the general chemical formula (III):
  • x is 1 -6, preferably 1 -4, more preferably 1 -3,
  • y is 1 -6, preferably 1 -4, more preferably 1 -2,
  • z is 0-6, preferably 0-4, more preferably 0-2.
  • the second silicone compound derived from an aqueous condensation wherein the aminoalkyltrihydroxysilane compound is (HO) 3 Si-(CH 2 ) 3 -NH 2 .
  • Dynasylan® SIVO 160 (CAS No. 1443627-61 -9) and Dynasylan® 1 151 (CAS No. 58160-99-9, 29159-37-3) available from Evonik, 3-Aminopropyl-silanetriol (CAS No. 58160-99-9) available from Gelest Inc, Silquest® A 1 106 (CAS No. 58160-99-9) available Momentive Performance Materials Inc., SiSiB®PC1 106 (CAS No. 58160-99-9) available from Power Chemical Corporation, may be used as one of the at least one second silicone compound.
  • a method of producing these compounds above is described in e.g. EP0675128B1 B1 , which are hereby incorporated. This compound is most responsible for the formation of a polymeric network matrix and then being effective as an anti fingerprint coating at low temperature.
  • the at least one acidifier may be any organic or inorganic acid. More preferably, the at least one acidifier is selected from the group comprising formic acid, oxalic acid, sulfuric acid, methacrylic acid, methane sulfonic acid and acetic acid. Furthermore, lactic acid, malic acid, glyceric acid, ortho-phosphoric acid, tartaric acid and succinic acid have in principle been proven acceptable to be used either. However, these latter acids are less preferred than formic acid, oxalic acid, sulfuric acid, methacrylic acid, methane sulfonic acid and acetic acid, because these latter acids may cause an impairment of the optical appearance of the chromium surface. Most preferably, acetic acid, formic acid and sulphuric acid are used.
  • the silicone coating mixture has a preferred pH of from 3.5 to 4.5, more preferably of about 3.5 ( ⁇ 0.2).
  • a pH of 4.5 yields lowest surface energy of the coated metal substrate and will therefore provide superior anti-fingerprint properties to the metal substrate.
  • lower pH promotes better optical finish of the anti fingerprint coating.
  • the resulting anti-fingerprint coating outside the preferred pH range of from 3.5 to 4.5 of the used mixture leads to declining fingerprint test results. Also it could be observed, if pH is lower than 3 or higher than 4.5, the life time of the silicone coating mixture is shortened.
  • the silicone coating mixture additionally contains at least one siloxane polymer.
  • the at least one siloxane polymer functions as surfactant and is in the following also named as SURF.
  • the at least one siloxane polymer is selected from the group consisting of compounds having general chemical formula (IV):
  • n is from 3 to 4
  • a is from 0 to 30;
  • b is from 0 to 30;
  • R is a hydrogen or alkyl radical of 1 to 4 carbon atoms.
  • (x+y) is from 1 to 20 where x is from 1 to 10 and y is from 0 to 10 and a is from 0 to 15; b is from 0 to 15; such that at least one of a and b is not zero and (a+b) is from 1 to 30.
  • the at least one siloxane polymer is siloxane block copolymer selected from the group consisting of polyethersiloxane-siloxane copolymers wherein (x+y) is from 2 to 60 where x is from 1 to 30 and y is 1 to 30, more preferably (x+y) is from 1 to 20 where x is from 1 to 10 and y is from 1 to 10 and a is from 0 to 15; b is from 0 to 15; such that at least one of a and b is not zero and (a+b) is from 1 to 30.
  • the silicone coating mixture may contain one siloxane polymer or a plurality of siloxane polymers, wherein these polymers may differ from each other by at least one of the parameters a, b and n.
  • the siloxane polymer has preferably a molecular weight of from 1 ,000 to 30,000 g/mole, preferably from 5,000 to 15,000 g/mole.
  • TEGO® Wet 280 (CAS No. 68938-54- 5)
  • TEGO® Wet 240 (CAS No. 67674-67-3)
  • TEGO® Wet 250 (CAS No. 27306-78-1 )
  • TEGO® Wet 270 (CAS No. 68938-54-5) available from Evonik® or Dimethylsiloxane-(50-55% ethylene oxide) block copolymer (CAS No. 68938-54-5) available from Gelest Inc.
  • Silwet® L 7600 (CAS No. 68938-54-5)
  • Silwet® L 77 (CAS No. 27306-78-1 ) available from Momentive Performance Materials Inc.
  • Metolat®342 (CAS No. 27306-78-1 ) available from Munzing Chemie GmbH
  • This compound is a wetting agent and further lowers surface energy of the coated metal substrate. It promotes drying of the coated metal substrate.
  • the silicone coating mixture contains the at least one first silicone compound and the at least one second silicone compound in a predetermined mass ratio, wherein the mass ratio of all first silicone compounds to all second silicone compounds is preferably from 1 .0 to 4.0, more preferably from 1 .0 to 1.0 and most preferably from 3.0 to 4.0.
  • the concentration of the at least one first silicone compound in the silicone coating mixture is from 0.05 g/l to 5.00 g/l, preferably from 0.10 g/l to 2.50 g/l and most preferably from 0.30 g/l to 1.50 g/l.
  • the concentration of the at least one second silicone compound in the silicone coating mixture is from 0.05 g/l to 10.00 g/l, preferably from 0.10 g/l to 3.00 g/l and most preferably from 0.40 g/l to 1.00 g/l.
  • the concentration of the at least one siloxane polymer in the silicone coating mixture is from 0.02 g/l to 5.00 g/l, preferably from 0.05 g/l to 1.00 g/l and most preferably from 0.10 g/l to 0.30 g/l.
  • bringing the metal substrate into contact with the silicone coating mixture is performed at a temperature of the silicone coating mixture of from 10 °C to 90 °C, more preferably from 20 °C to 70 °C and most preferably at about 50 °C ( ⁇ 5 °C).
  • exposure time of the metal substrate to the anti-fingerprint coating solution is from 0.5 min to 60 min, more preferably from 1 min to 20 min and most preferably from 1 min to 2 min.
  • curing of the coated metal substrate is performed at a temperature of from 20 °C to 100 °C, more preferably from 40 °C to 90 °C and most preferably from 60 °C to 80 °C for a duration of 5 min to 120 min, more preferably from 15 min °C to 90 min °C and most preferably from 30 min to 60 min.
  • the metal substrate In order to coat the metal substrate with the anti-fingerprint coating, it is brought into contact (treated) with the silicone coating mixture.
  • the treated metal substrate In a first alternative of the method, the treated metal substrate is partially dried and thereafter rinsed with water (wet-in-wet rinsing method) in order to remove excess silicon coating mixture at geometrically disadvantaged parts for avoiding optical defects. The treated and rinsed metal substrate is finally cured.
  • the treated metal substrate is dried without rinsing it (dry withdrawal method) and finally cured.
  • the first alternative is quick and easy to perform. However, part of the adsorbed silicone species is in this case desorbed again in the rinsing step.
  • the metal substrate is brought into contact with the silicone coating mixture by dipping it into the coating mixture and left therein for a predetermined period of time. Thereafter either the substrate (coating by substrate withdrawal) or the silicone coating mixture (coating by drainage is removed from the plating tank. More preferably, the coating application is performed at a constant (linear) withdrawal or drainage speed. Even more preferably the withdrawal/drainage speed is at least 1 mm/min, more preferably at least 50 mm/min and most preferably at least 10 mm/min. Furthermore, withdrawal speed is preferably at most 1000 cm/min, more preferably at most 500 cm/min and most preferably at most 100 cm m/min.
  • the silicone coating mixture may be applied using methods conventional in plating industry, i.e., in a dip tank as described hereinbefore or in a conveyorized treatment plant wherein workpieces to be treated are conveyed from one treatment station to the next one.
  • the method of the present invention comprises basically the step of treating the metal substrate with the silicone coating mixture and a curing step and optionally also a rinsing step (bringing the metal substrate into contact with water)
  • the conveyorized plant would comprise a first station for treating the metal substrate with the silicone coating mixture and an optional second station wherein the metal substrate is rinsed and, optionally, a third station wherein the coated metal substrate is cured .
  • Anti-fingerprint action of the anti-fingerprint coating will have an effect on surface energy of the coated metal substrate.
  • the surface energy can be measured indirectly by measuring contact angle of a test liquid which is brought into contact with the coated metal substrate.
  • Contact angle measurement methods are well-known and for example are described in Law and Zhao, Surface Wetting - Characterization, Contact Angle and Fundamentals, Springer Verlag (2016) ISBN 9783319252124.
  • Another approach for determining the effect of the anti-fingerprint coating on the metal substrate is to assess the ability of the coated metal substrate to withstand soiling of the surface thereof with human exudation and/or human sebum and/or to overcome such soiling when the contaminated surface is tried to be cleaned mechanically.
  • exemplary testing conditions may be set up to investigate the effect of an anti-fingerprint coating produced with the method of the present invention. For example, an artificial exudation specimen with predetermined composition is applied in a reproducible manner, by stamping same at a predetermined force, to the metal substrate surface, with a silicone stamp for example.
  • Mechanical removal of the exudation / sebum may likewise by reproducibly be tested by wiping the artificial fingerprint with a cloth of predetermined quality, a microfiber cloth for example, at a predetermined force, predetermined wiping speed and movement, a circular movement for example, and for a predetermined number of wiping events.
  • the effect of the contamination of the metal substrate surface and removal efficiency may finally be determined by determining and comparing the color differences using L/a/b coordinates with a spectrophotometer before and after application of the test.
  • a smaller difference in the initial and final colors indicates less sensitivity of the surface against fingerprints. For example a DI_ value larger than 2.5 units and/or Ab value larger than 1 .75 units on a test spot are easily distinguished as a flake by human eye, whereas smaller values become less visible under normal light conditions.
  • Fig: 1 shows a diagram displaying contact angle values for samples treated in solutions of single compounds; for comparison, a standard composition (Std: silicone coating mixture according to the invention) is included in the graph (0.9 / 0.3 / 0.2 g/l for CMPD B / CMPD A / SURF);
  • Fig. 2 shows a diagram displaying fingerprint test results for samples OA-OE in the form of AUAa/Ab values measured before and after application and cleaning of a fingerprint
  • Fig. 3 shows a diagram displaying contact angle values for samples treated in silicone coating mixtures containing CMPD B and CMPD A with and without surfactant (SURF);
  • Fig. 4 shows a diagram displaying fingerprint test results for samples treated in silicone coating mixtures containing CMPD B and CMPD A with and without surfactant (SURF) in the form of AUAa/Ab values measured before and after application and cleaning of a fingerprint;
  • SURF surfactant
  • Fig. 5 shows a diagram displaying contact angle values for samples treated in silicone coating mixtures at different pH; pH was adjusted by the addition of acetic acid;
  • Fig. 6 shows a diagram displaying fingerprint test results for samples treated in solutions at different pH
  • Fig. 7 shows a diagram displaying contact angle values for samples treated in silicone coating mixtures that contained different types of acids for pH adjustment
  • Fig. 8 shows a diagram displaying contact angle values of samples treated in silicone coating mixtures that contained different combinations of CMPD B and CMPD A;
  • Fig. 9 shows a diagram displaying fingerprint test results for samples treated in silicone coating mixtures that contained different combinations of CMPD B and CMPD A;
  • Fig. 10 shows a diagram displaying contact angle values on various chromium substrates after treatment with a silicone coating mixture
  • Fig. 1 1 shows a diagram displaying fingerprint test results on various chromium substrates after treatment with a silicone coating mixture
  • Fig. 12 shows a diagram displaying contact angle values of samples treated in silicone coating mixtures at different temperatures
  • Fig. 13 shows a diagram displaying contact angle values of samples treated with a silicone coating mixture and cured successively at 70 °C for various curing durations
  • Fig. 14 shows a diagram displaying fingerprint test results on samples treated with a silicone coating mixture and cured successively at 70 °C for various curing durations
  • Fig. 15 shows a diagram displaying contact angle values of samples withdrawn from a silicone coating mixture at various speeds
  • Fig. 16 shows a diagram displaying fingerprint test results on samples withdrawn from the silicone coating mixture at various speeds
  • Fig. 17 shows a schematic workflow for a fingerprint test.
  • Hull Cell plates were prepared using the following procedure: i. Satin Ni deposition in Satilume® Plus (trademark of Atotech GmbH) bath (coating thickness 12 - 15 pm);
  • Chromium deposition from trivalent chromium bath Trichrome® Plus (trademark of Atotech GmbH) (coating thickness 0.4 - 0.6 pm).
  • Satilume® Plus bath is an electroplating bath for depositing satin nickel coatings. It is based on NiS04, NiCI2, and boric acid as the main components and organic additives to create the satin appearance. Nickel was deposited under the following conditions: T: 51 °C, pH: 4.1 , current density: 4 A/dm 2 , plating time 15 min.
  • Trivalent chromium bath Trichrome® Plus is a chloride containing electroplating bath for depositing light chromium coatings. It is based on basic chromium sulfate, boric acid as buffering agent, a carboxylic acid based complexing agent and halide based conductivity salts... as the main components. Chromium is electrodeposited using this bath complying with the following plating conditions: T: 35 °C, pH: 2.8, current density: 10 A/dm 2 , plating time 2 min.
  • Cr 843 is based on Cr0 3 and on sulfate and SiF 6 containing catalysts. Chromium is electrodeposited using this bath complying with the following plating conditions: T: 40 °C, current density: 10 A/dm 2 , plating time 3 min.
  • Trichrome® ICE is based on basic chromium sulfate, boric acid as buffering agent, a carboxylic acid based complexing agent and sulfate based conductivity salts. Chromium is electrodeposited using this bath complying with the following plating conditions: T: 55 °C, pH: 3.5, current density: 5 A/dm 2 , plating time 10 min.
  • Trichrome® Smoke 2 is based on basic chromium sulfate, boric acid as buffering agent, a carboxylic acid based complexing agent and halide based conductivity salts and sulfur containing darkening agents. Chromium is electrodeposited using this bath complying with the following plating conditions: T: 35 °C, pH: 2.8, current density: 10 A/dm 2 , plating time 5 min.
  • Trichrome® Graphite is based on basic chromium sulfate, boric acid as buffering agent, a carboxylic acid based complexing agent and halide based conductivity salts and sulfur containing darkening agents. Chromium is electrodeposited using this bath complying with the following plating conditions: T: 35 °C, pH: 3.2, current density: 10 A/dm 2 , plating time 5 min.
  • a standard composition of the silicone coating mixture comprises the following components:
  • CMPD A is a first silicone type compound derived from an aqueous co-condensation of at least two monomeric building blocks selected from the group consisting an aminoalkyltrihydroxysilane compound and a fluoroalkylalkyltrihydroxysilane compound, wherein the aminoalkyltrihydroxysilane compound has the general chemical formula (I):
  • This silicone compound is used in the form of a 15 wt.-% solution of this compound in water acidified with formic acid to pH 4.
  • CMPD B is a second silicone type compound and is a water soluble polymeric aminoalkylsilicone compound which is derived from aqueous condensation of at least one monomeric building block selected from the group consisting of a aminoalkyltrihydroxysilane compound, wherein the aminoalkyltrihydroxysilane compound has the general chemical formula (III):
  • This second silicone compound is used in the form of a 10 wt.-% solution of this compound in water acidified with formic acid to pH 4.
  • siloxane polymer (SURF) is used as a siloxane block copolymer (CAS No. 68938-54-5) in the form of a 10 wt.-% solution of this compound in water. If not stated otherwise, temperature of the silicone coating mixture during the step of treating the metal substrate was fixed to 25 °C.
  • the substrates Prior to sol-gel application, the substrates were cleaned in a cathodic degreasing bath UniClean® 256 (trademark of Atotech GmbH, Germany; alkaline degreasing bath) for 1 min at 10 ASD (A/dm 2 ) and thoroughly rinsed with deionized water afterwards. Wet substrates were immersed into the silicone coating mixture in a 500 ml glass beaker.
  • UniClean® 256 trademark of Atotech GmbH, Germany; alkaline degreasing bath
  • Immersion and withdrawal of samples were done with the aid of a dip coating robot that allowed to control immersion and withdrawal speed (immersion speed: 100 cm/min; immersion time: 1 min; immersion depth: 8 cm (lower edge of a specimen below liquid level); withdrawal speed: 5 cm/min (if not stated otherwise)).
  • L * indicates lightness and a * and b * indicate color directions.
  • a positive value 25 of a * indicates a red color while a negative value of a * means a green color.
  • a positive value of b * indicates a yellow color and a negative value of b * means a blue color.
  • the value of L * ranges from zero to 100, wherein zero indicates black and 100 means white.
  • Table 1 gives the set-up parameters for producing the test samples.
  • CMPD A and CMPD B have relatively small but remarkable effect on surface energy. Minimum surface energy is acquired after treatment in CMPD B solution, yielding a contact angle of 55.5°. CMPD A yields a contact angle of around 30° only, even though this component comprises fluorinated functional groups that would be expected to result in low surface energy. Though not being bound by theory, it is believed that CMPD A cannot be adsorbed properly on the surface if this component is not supported by other organosilicon compounds that anchor it on the chromium surface strongly.
  • Table 3 lists the results from fingerprint measurements:
  • results of the fingerprint test are demonstrated in Fig. 2.
  • the test results are in line with the contact angle measurements. More hydrophobic surfaces repel dirt and are easier to clean. Consequently, L/a/b values have a smaller shift from the original color after application of the artificial fingerprint. The shift is more pronounced for L and b values whereas the a value is less effected in this test.
  • the untreated sample (OA) reveals -4.0 and 2.3 units shift in L and b values respectively.
  • Similar AUAb values were measured on samples that were treated in acetic acid (OB) and SURF (OE) solutions. The color shift became smaller after treatment in CMPD A (OC) and CMPD B (OD) solutions. Treatment in the standard composition that contained all components yielded AUAa/Ab values of -2.4/0.2/1.6, resp.
  • Table 4 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water.
  • Table 5 lists the results from contact angle measurements for these samples.
  • Table 6 lists the results from fingerprint measurements in this Experimental Set.
  • Fig. 3 shows the measured contact angle values on the related samples.
  • the silicone coating mixture yielded a lower surface energy compared to the single components (larger contact angle). Contact angle values between 75 - 90° were achieved due to treatment in the silicone coating mixtures.
  • Table 7 gives the set-up parameters, including pH values, for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 8 lists the results from contact angle measurements for these samples. Table 9 lists the results from fingerprint measurements in this Experimental Set. pH of the silicone coating mixture was adjusted by addition of acetic acid.
  • Table 10 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 1 1 lists the results from contact angle measurements for these samples. Table 12 lists the results from fingerprint measurements in this Experimental Set.
  • Acetic acid, formic acid and sulfuric acid were shown not to cause any discoloration on the surface even if post-rinsing was applied.
  • acetic acid and formic acid yielded slightly lower coating surface energy.
  • Acetic acid was favored due to easier handling.
  • Table 13 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 14 lists the results from contact angle measurements for these samples. Table 15 lists the results from fingerprint measurements in this Experimental Set.
  • CMPD B content was further decreased up to 1 14° by reducing CMPD B content furthermore to about half this amount (0.5 g/l CMPD B / 1.5 g/l CMPD A).
  • CMPD B content had a negative influence and increased surface energy as was observed for 0.2 g/l CMPD B / 1.5 g/l CMPD A.
  • CMPD B concentration should be kept above a critical value, ideally above 0.3 g/l. It is believed that this would support CMPD A co-adsorption sufficiently. It has proved that surface energy of the coating remains constant independent of film thickness, once a compact coating has formed. Theoretically, film thickness grew by increasing total silicone concentration in the coating mixture.
  • Table 16 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 17 lists the results from contact angle measurements for these samples. Table 18 lists the results from fingerprint measurements in this Experimental Set.
  • Temperature of the coating mixture has proven an important parameter which has shown to be responsible not only for kinetic activity of the components but also for drying speed of the substrate after its withdrawal from the silicone coating mixture.
  • the temperature of the coating mixture was gradually increased to investigate its effect on coating quality.
  • Table 19 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 20 lists the results from contact angle measurements for these samples.
  • Table 21 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 22 lists the results from contact angle measurements for these samples. Table 23 lists the results from fingerprint measurements in this Experimental Set.
  • Fingerprint test results (Fig. 14) also hint for two regions below and above 60 min curing duration. Above 60 min, removal of the artificial fingerprint was shown to be easier and to leave less residues behind as was deduced from AUAa/Ab values.
  • Table 24 gives the set-up parameters for producing the samples in this Experimental Set. Again, as described for the First Experimental Set, all treatment compositions were prepared as given in this Table by specifying that the respective components are added to give 1 I, wherein the remainder is water. Table 25 lists the results from contact angle measurements for these samples. Table 26 lists the results from fingerprint measurements in this Experimental Set.
  • Film thickness increases with evaporation speed that becomes higher in relation to withdrawal speed when the substrate is moved very slowly, whereas it becomes lower in relation to withdrawal speed when the substrate is moved out quickly. Assuming below a certain thickness, film thickness and hydrophobicity are directly correlated to each other. Therefore, a good match between proposed theory and the results of the present investigation is found.
  • Coating quality can be tested by contact angle measurements. Fingerprint test results are usually in line with the contact angle results. However, contact angle measurements are more reproducible and much easier to apply.
  • CMPD B is believed to behave as the matrix of the anti-fingerprint coating. Providing a sufficient amount of CMPD B, the other main component CMPD A is achieved to be better anchored on the chromium surface and better incorporated into the coating network.
  • CMPD A is believed to be the main hydrophobing agent in the formulation. Increasing CMPD A amount results in formation of more hydrophobic and dirt repelling coatings.
  • CMPD A can be added separately to the coating mixture for improving the repelling effect of the coating.
  • the surfactant SURF improves film homogeneity and reduces the number of optical defects on the coating.
  • Adjusting bath pH is required by the addition of some acid into the bath. At the original pH of the coating mixture (without the addition of any acid), more defects on the coating were observed. At pH 3.5, the number of defects significantly reduced. Adjusting the pH to more acidic values resulted in better coating quality, but a low pH value negatively influenced stability of the coating mixture by decreasing hydrolysation rate and by increasing condensation rate of the dissolved silicone compounds.
  • acetic acid has proven to be the best compound to use.
  • formic acid and sulphuric acid can also be employed.
  • Other tested acids such as phosphoric acid, malic acid and glyceric acid, also work principally well, but they may cause discoloration on the surface under certain circumstances.
  • the method of the present invention performs better on bright chromium deposits than on dark chromium deposits. When the deposit contains more alloying elements and becomes darker, hydrophobicity and dirt repelling effect gradually decreases. Coating quality significantly increases with increasing temperature of the coating mixture. Another big advantage of high temperature of the coating mixture is the possibility to increase withdrawal speed due to faster drying of the dip coat.
  • the applied sol-gel anti-fingerprint coating must be cured for achieving best performance. A longer curing duration results in a more compact film. Saturation has proven to reach after 60 min.
  • the coating mixture performs slightly better after heating it. Activation of the coating mixture is kept for some time even after the coating mixture is cooled down again.
  • a certain amount of artificial skin fat is applied onto a test surface with the aid of a silicon stamp. Consequently, the applied fingerprint is removed with a microfiber cloth to evaluate the ability of the surface to be cleaned easily.
  • Sample preparation The sample had a minimum surface area of 25 cm 2 . Samples were measured as received, unless they were excessively contaminated. Visible dust particles and other dirt were gently removed from the surface before the application of the test. Only dry samples were measured.
  • a silicon stamp was used to apply an artificial fingerprint onto a sample surface. To prepare the stamp, prior to each measurement the silicon stamp was cleaned by immersion into isopropanol by immersing same into this solvent for 10 seconds minimum and then drying it.
  • the ability of the substrate to be cleaned from of the fingerprint is evaluated by rubbing the stamped areas with a microfiber cloth.
  • typical cleaning gesture is mimicked.
  • the cloth was wrapped around the forefinger of the preferred hand.
  • the fingerprint is rubbed with circular movements.
  • Applied force for rubbing is approximately 5 N - finger force was tested on a laboratory scale by targeting 500 g measured weight during movements. Rubbing speed is not significantly influential on the test result.
  • An unused microfiber cloth is always employed for cleaning. 20 rubbing cycles were applied in total (Fig. 17: Cleaning with a cloth. 40 circular cycles). After 20 cycles, L/a/b values were measured on the cleaned area again. Differences in the color parameters, AUAa/Ab, between before soiling / cleaning and thereafter were used for evaluation of the easy-to-clean properties.

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  • Application Of Or Painting With Fluid Materials (AREA)
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  • Paints Or Removers (AREA)
  • Detergent Compositions (AREA)
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Abstract

L'invention concerne des revêtements anti-empreintes digitales permettant d'obtenir des propriétés anti-empreintes digitales sur des surfaces décoratives, ainsi qu'un nouveau procédé de revêtement d'un substrat métallique avec un revêtement anti-empreintes digitales. Le procédé comprend les étapes consistant à : (a) fournir le substrat métallique; (b) fournir un mélange de revêtement de silicone contenant : (i) au moins un premier composé de silicone choisi dans le groupe constitué par des silicones mono ou oligo(aminoalkyle)-fluoroalkyle; (ii) au moins un second composé de silicone choisi dans le groupe constitué par les silicones aminoalkyles; (iii) au moins un acidifiant; et (iv) de l'eau; en outre (c) traiter le substrat métallique avec le mélange de revêtement de silicone en amenant le substrat métallique au contact du mélange de revêtement de silicone; et (d) durcir le substrat métallique traité à une température prédéfinie.
PCT/EP2019/063294 2018-05-24 2019-05-23 Revêtements anti-empreintes digitales WO2019224286A1 (fr)

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