EP1874882A1 - Procede pour produire une couche protectrice permanente sur des surfaces en metal precieux par enduction avec des solutions a base de polysilazane - Google Patents

Procede pour produire une couche protectrice permanente sur des surfaces en metal precieux par enduction avec des solutions a base de polysilazane

Info

Publication number
EP1874882A1
EP1874882A1 EP06700885A EP06700885A EP1874882A1 EP 1874882 A1 EP1874882 A1 EP 1874882A1 EP 06700885 A EP06700885 A EP 06700885A EP 06700885 A EP06700885 A EP 06700885A EP 1874882 A1 EP1874882 A1 EP 1874882A1
Authority
EP
European Patent Office
Prior art keywords
polysilazane
silver
coating
metal
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06700885A
Other languages
German (de)
English (en)
Inventor
Stefan Brand
Andreas Dierdorf
Hubert Liebe
Andreas Wacker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP1874882A1 publication Critical patent/EP1874882A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to a method for producing a permanent protective layer on precious metal surfaces, in particular silver surfaces to prevent tarnishing.
  • Coated with precious metal surfaces, deposited by electroplating, for example, form a layer of sulfide and oxide in the air, forming yellowish, brownish to black, spotty deposits depending on the duration of exposure, commonly referred to as “tarnishing" "Start-up” is additionally intensified by chemical influences, such as skin contact (sweat, body fat, etc.) or contact with food and drink.
  • tarnishing spotty deposits depending on the duration of exposure
  • start-up is additionally intensified by chemical influences, such as skin contact (sweat, body fat, etc.) or contact with food and drink.
  • Another method of preventing tarnishing is coating the consumer article with a polymer dispersion.
  • Polymer dispersions form on the surface a polymer film which protects silver from tarnishing.
  • these polymer films are not scratch resistant and do not permanently stay on the surface of the object. By use, the polymer film is removed and the article starts running.
  • This problem is basically related to insufficient adhesion of coatings to silver and other precious metal surfaces, and is particularly noticeable on surfaces that have high silver content (> 95%) (eg, silver plated articles).
  • the object of the present invention is therefore to provide a method which makes it possible to produce a permanent protective layer also on precious metals.
  • polysilazanes are also suitable for a permanent protective layer to prevent start-up of noble metal surfaces, in particular silver surfaces, if a silane-based primer is previously applied which improves the adhesion of the polysilazane coating.
  • the present invention thus achieves the stated object and relates to a method for coating surfaces of noble metal or noble metal alloys with a solution comprising a polysilazane of the formula 1 (first polysilazane layer)
  • n is such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol, and a solvent and a catalyst, and before coating with the polysilazane solution, a sulfur-based silane-based primer is applied to the article to be coated to improve adhesion becomes.
  • This primer also makes it possible to coat precious metal surfaces that would otherwise not provide sufficient polysilazane adhesion, such as silver surfaces with> 95% silver or gold surfaces.
  • the primer is silanes containing a thiol, disulfide or tetrasulfide function which provides for a firm anchoring of the polysilazane on the silver surface.
  • precious metals are understood as meaning the pure metals or alloys of noble metals having a noble metal content of at least 60%, preferably 70%, in particular> 75%.
  • a noble metal is understood here to mean a metal whose normal potential ⁇ 0 (in volts) according to the electrochemical voltage series has a value of> 0.3 volts compared to the standard hydrogen electrode (0 volts). These are, for example, copper, silver, gold, platinum, palladium, rhodium, iridium, ruthenium, osmium.
  • the silane-based primer used in the present invention contains at least one silane having a sulfur-containing functional group.
  • Silanes of the formula 2 to 4 or mixtures of these silanes are particularly suitable
  • R is the same or different and R is an alkyl radical, in particular a methyl, ethyl, propyl or alkoxy radical, in particular a methoxy, ethoxy or propoxy radical.
  • the primer is usually in diluted form, i. used as a solution in an organic solvent such as alcohol, ketone, ether or ester and mixtures of these solvents.
  • the solution may also contain other ingredients such as water, acids or bases.
  • concentration of the silanes of the formula (2) to (4) in the primer solution is 0.1 to 50%, preferably 0.5 to 10%, particularly preferably 1 to 3%.
  • the function of the silane primer is to provide a solid compound of the polysilazane with the noble metal surface.
  • the sulfur-containing functional groups of the silane primer have high affinity for and can bond permanently to noble metal surfaces, while the silane groups have high affinity for and also become permanently attached to the polysilazane.
  • the excess primer is washed off with water or a solvent, and then the residual solvent is evaporated. This can be done either at room temperature or in a drying oven at elevated temperature and the polysilazane coating applied. Depending on the polysilazane used, solvent and catalyst, this is then dried at room temperature or in a drying oven.
  • the proportion of polysilazane in the solvent is from 1 to 50% by weight of polysilazane, preferably from 3 to 30% by weight, particularly preferably from 5 to 20% by weight.
  • Particularly suitable solvents for the polysilazane are organic solvents which contain no water and no reactive groups (such as hydroxyl or amine groups). These are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and mono- and polyalkylene glycol dialkyl ethers (glymes) or mixtures of these solvents.
  • organic solvents which contain no water and no reactive groups (such as hydroxyl or amine groups). These are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl
  • Another component of the polysilazane formulation may include additives, e.g.
  • Influencing influence or inorganic nanoparticles such as
  • the catalysts used may be, for example, organic amines, acids or metals or metal salts, preferably metal carboxylates or acetylacetonates or mixtures of these compounds.
  • the catalyst is preferably used in amounts of 0.001 to 10%, in particular 0.01 to 6%, particularly preferably 0.1 to 3%, based on the weight of the polysilazane.
  • amine catalysts are ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, di-n-propylamine, di-isopropylamine, tri-n-propylamine, n-butylamine, isobutylamine, di-n-propylamine.
  • organic acids examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid.
  • metals and metal compounds as catalysts are palladium, palladium acetate, palladium acetylacetonate, palladium propionate, nickel, nickel acetylacetonate, silver, silver acetate, silver acetylacetonate, platinum,
  • the presence of moisture or oxygen may play a role in the cure of the coating.
  • the rapid curing at high or low humidity or at high or low oxygen content can be achieved.
  • the person skilled in these influences are known and he will adjust the atmospheric conditions by appropriate optimization methods.
  • the second layer can be a polysilazane of the formula 1 or else substituted polysilazanes which carry one or two organic groups such as, for example, methyl, ethyl, propyl, vinyl, phenyl or trialkoxysilyl-substituted alkyl groups instead of the hydrogen atoms on the silicon or on the nitrogen ,
  • Such polysilazanes and the preparation of these polysilazanes is described for example in US 6,329,487, US 6,652,978 or US 6,534,184. These documents are hereby incorporated by reference.
  • Another object of the invention are coatings for precious metal surfaces, in particular silver surfaces, which are produced by the method according to the invention.
  • Examples of surfaces of silver and silver alloys that can be coated according to the invention are silver jewelry with a silver content of 75 to 99%, preferably with a silver content of 80 and 92.5% (800 silver and 925 sterling silver) such as polished Silver jewelry, frosted silver jewelry, brushed silver jewelry, diamond-cut silver jewelry with and without gemstones such as diamonds, gemstones, semi-precious stones and glass.
  • silver plated surfaces are products having a silver coating of 1 to 100 microns, preferably silver plated or silver plated with a silver coating of 18 microns or a 36 micron silver coating, ie 90 grams of silver per 1000 grams Product (80's silver) for example for silvered cutlery.
  • the following examples describe the preparation of an adherent protective layer using the primer.
  • the polysilazane solutions used are perhydropolysilazane solutions from Clariant Japan K.K.
  • the solvent used is di-n-butyl ether (designated NL).
  • the solution contains (0.75 wt.%) Palladiumpropionat based on the perhydropolysilazane as a catalyst.
  • Example 1 Coating of a silver sheet (99.9%) with prior primer using a sulfur-containing primer
  • a silver sheet with a silver content of 99.9% is degreased by rinsing with isopropanol and immersed in a primer solution of the following composition ( % By weight): 3- (trimethoxysilyl) -1-propanethiol 2%, isopropanol 88%, water 9.4%, glacial acetic acid 0.6%.
  • a primer solution of the following composition ( % By weight): 3- (trimethoxysilyl) -1-propanethiol 2%, isopropanol 88%, water 9.4%, glacial acetic acid 0.6%.
  • excess primer solution is rinsed with isopropanol and adhering isopropanol was evaporated in a drying oven (130 0 C, 5 min).
  • the silver plate After cooling to room temperature, the silver plate is immersed for 1 min in a polysilazane solution (20% in dibutyl ether, contains palladium catalyst) and slowly pulled out of the polysilazane solution. Excess drops of polysilazane solution are removed with a cloth. After evaporation of dibutyl ether (10 min, room temperature), the polysilazane-coated silver sheet is cured in a drying oven (130 0 C, 3 h).
  • a polysilazane solution 20% in dibutyl ether, contains palladium catalyst
  • Example 2 Coating a silver spoon (silver plated) with prior primer using a sulfur-containing primer
  • a silver spoon (silvered, silver content of the silver coating> 99%) is degreased by rinsing with isopropanol and immersed for one hour in a primer solution of the following composition (% by weight): 3- (trimethoxysilyl) -1-propanethiol 2%, isopropanol 88%, water 9.4%, glacial acetic acid 0.6%.
  • a primer solution of the following composition (% by weight): 3- (trimethoxysilyl) -1-propanethiol 2%, isopropanol 88%, water 9.4%, glacial acetic acid 0.6%.
  • the silver spoon After cooling to room temperature, the silver spoon is immersed for 1 min in a polysilazane solution (20% in dibutyl ether, contains palladium catalyst) and slowly pulls it out of the polysilazane solution. Excess drops of polysilazane solution are removed with a cloth. After evaporation of dibutyl ether (10 min, room temperature), the polysilazane-coated silver spoon is cured in a drying oven (130 0 C, 3 h).
  • Comparative Example 1 Coating of a silver sheet (99.9%) without priming A silver sheet with a silver content of 99.9% is degreased or cleaned by rinsing with isopropanol. Adhesive isopropanol is removed in a drying oven (13O 0 C, 5 min). After cooling to room temperature, the silver plate is immersed for 1 min in a polysilazane solution (20% in dibutyl ether, contains palladium catalyst) and slowly pulled out of the polysilazane solution. Excess drops of polysilazane solution are removed with a cloth. After evaporation of dibutyl ether (10 min, room temperature), the polysilazane-coated silver sheet is cured in a drying oven (130 0 C, 3 h).
  • Comparative Example 2 Coating of a silver spoon (silvered) without priming
  • a silver spoon (silvered, silver content of the silver coating> 99%) is degreased or cleaned by rinsing with isopropanol.
  • Adhesive isopropanol is removed in a drying oven (13O 0 C, 5 min). After cooling to room temperature, the silver spoon is immersed for 1 min in a polysilazane solution (20% in dibutyl ether, contains palladium catalyst) and slowly pulls it out of the polysilazane solution. Excess drops of polysilazane solution are removed with a cloth.
  • a silver plate with a silver content of 99.9% is degreased by rinsing with isopropanol and immersed for 1 min in an AMEO primer solution of the following composition (wt .-%): 3- (triethoxysilyl) propylamine (AMEO) 1% , Isopropanol 98.5%, water 0.5%.
  • AMEO primer solution of the following composition (wt .-%): 3- (triethoxysilyl) propylamine (AMEO) 1% , Isopropanol 98.5%, water 0.5%.
  • the silver plate rinsed with water and dried in a drying oven (13O 0 C, 5 min).
  • the silver plate is immersed for 1 min in a polysilazane solution (20% in dibutyl ether, contains
  • Example 3 Determination of adhesion by Tesa test The adhesion of the polysilazane coatings of Examples 1 and 2 and of Comparative Examples 1 to 3 to silver is tested by applying and removing a TesafilmstMails on the polysilazane coating. The following result is obtained:
  • Example 1 and 2 no detachment of the coating observed very good adhesion of the coating on silver
  • Comparative Examples 1 to 3 clear softening of the coating, partial complete detachment of the coating
  • Example 4 Determination of Resistance to Hydrogen Sulfide The tarnish protection of the polysilazane-coated silver objects (silver plate, silvered spoon) of Examples 1 and 2 compared to uncoated silver objects was tested by aging in a sample chamber into which H 2 S had been metered. After six hours of paging, the following was observed: coated: no discoloration to recognize

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour enduire des surfaces en métal précieux ou en alliages de métal précieux avec une solution contenant un polysilazane de formule (1), dans laquelle n est calculé, de sorte que le polysilazane présente un poids moléculaire moyen en nombre de 150 à 150 000 g/mol, ainsi qu'un solvant et un catalyseur. Ce procédé se caractérise en ce qu'un primaire à base de silane, contenant du soufre et destiné à améliorer l'adhérence, est appliqué sur l'objet à enduire avant l'enduction avec la solution de polysilazane. Cette invention concerne également des revêtements réalisés par le procédé de l'invention.
EP06700885A 2005-01-26 2006-01-12 Procede pour produire une couche protectrice permanente sur des surfaces en metal precieux par enduction avec des solutions a base de polysilazane Withdrawn EP1874882A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005003627A DE102005003627A1 (de) 2005-01-26 2005-01-26 Verfahren zur Erzeugung einer permanenten Schutzschicht auf Edelmetalloberflächen durch Beschichten mit Lösungen auf Polysilazanbasis
PCT/EP2006/000213 WO2006079451A1 (fr) 2005-01-26 2006-01-12 Procede pour produire une couche protectrice permanente sur des surfaces en metal precieux par enduction avec des solutions a base de polysilazane

Publications (1)

Publication Number Publication Date
EP1874882A1 true EP1874882A1 (fr) 2008-01-09

Family

ID=36095874

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06700885A Withdrawn EP1874882A1 (fr) 2005-01-26 2006-01-12 Procede pour produire une couche protectrice permanente sur des surfaces en metal precieux par enduction avec des solutions a base de polysilazane

Country Status (10)

Country Link
US (1) US20080118651A1 (fr)
EP (1) EP1874882A1 (fr)
JP (1) JP2008528328A (fr)
KR (1) KR20070102568A (fr)
AU (1) AU2006208563A1 (fr)
BR (1) BRPI0607090A2 (fr)
CA (1) CA2595911A1 (fr)
DE (1) DE102005003627A1 (fr)
NO (1) NO20074290L (fr)
WO (1) WO2006079451A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005051755A1 (de) * 2005-10-27 2007-05-10 Clariant International Limited Verfahren zur Verbesserung der Korrosionsbeständigkeit und Lichtechtheit von gefärbten Aluminiumoxidschichten
US7967476B2 (en) * 2007-07-04 2011-06-28 Nichia Corporation Light emitting device including protective glass film
ES2736731T3 (es) 2008-07-18 2020-01-07 Suneeta Neogi Método para producir recubrimientos de diamante nanocristalino sobre piedras preciosas
WO2011109807A2 (fr) * 2010-03-05 2011-09-09 Serenity Technologies, Inc. Procédé pour conférer une protection contre le ternissement ou une protection contre le ternissement avec un aspect coloré à l'argent, aux alliages de l'argent, aux films d'argent, aux produits en argent et autres métaux non précieux
CN103180257B (zh) * 2010-11-17 2016-02-17 3M创新有限公司 减少银的电迁移的方法及由其制备的制品
JP5130408B1 (ja) * 2011-12-27 2013-01-30 株式会社ジュエリー・ミウラ 貴金属保護膜の形成方法
JP6232792B2 (ja) * 2013-07-17 2017-11-22 日亜化学工業株式会社 発光装置

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US4618688A (en) * 1985-04-12 1986-10-21 Scm Corporation Silane compositions
US6383641B1 (en) * 1997-08-15 2002-05-07 Asahi Glass Company Ltd. Transparent coated molded product and method for producing the same
US6534184B2 (en) * 2001-02-26 2003-03-18 Kion Corporation Polysilazane/polysiloxane block copolymers
MXPA05004659A (es) * 2002-11-01 2005-06-08 Clariant Int Ltd Solucion de revestimiento que contiene polisilazano.
DE10320180A1 (de) * 2003-05-07 2004-06-24 Clariant Gmbh Verwendung von Polysilazan als permanenter Anlaufschutz für Bedarfsgegenstände aus Silber und Silberlegierungen sowie für versilberte Bedarfsgegenstände
CN100567356C (zh) * 2003-10-06 2009-12-09 3M创新有限公司 抗污聚氨酯涂料

Non-Patent Citations (1)

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Title
See references of WO2006079451A1 *

Also Published As

Publication number Publication date
WO2006079451A1 (fr) 2006-08-03
CA2595911A1 (fr) 2006-08-03
JP2008528328A (ja) 2008-07-31
DE102005003627A1 (de) 2006-07-27
US20080118651A1 (en) 2008-05-22
AU2006208563A1 (en) 2006-08-03
BRPI0607090A2 (pt) 2009-08-04
NO20074290L (no) 2007-08-22
KR20070102568A (ko) 2007-10-18

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