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
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
  • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/54—Electroplating of non-metallic surfaces
  • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

• the present invention relates to a photosensitive dispersion with adjustable viscosity for depositing metal on an insulating substrate and to its use.
• Applicant's patent EP 0 687 311 relates to a polymeric resin with adjustable viscosity and pH for the deposition of catalytic palladium on a substrate, comprising, in combination, a palladium salt, a complexing agent of the carboxylic acid or chloride type, a polymer containing water-soluble hydroxyl and / or carboxyl groups, a basic compound and a solvent chosen from water, methanol and ethanol, the pH value being between 1 and 10, as well as in its applications for the deposition of catalytic palladium on the substrate surface and for the metallization of these surfaces.
• One of the essential aims of the present invention therefore consists in remedying the aforementioned drawbacks and in presenting a photosensitive dispersion with adjustable viscosity which no longer necessarily requires the use of a noble metal such as palladium and which also calls for other more common and less expensive metals whose photosensitivity is extended to a range of wavelengths between 190 and 450 nm and requiring a much lower irradiation energy than the polymeric resins known up to now, less than 100 mJ / cm 2 and not requiring the obligatory passage by an autocatalytic bath for the metallization of the substrate, allowing therefore a direct electrolytic metallization.
• a noble metal such as palladium
• other more common and less expensive metals whose photosensitivity is extended to a range of wavelengths between 190 and 450 nm and requiring a much lower irradiation energy than the polymeric resins known up to now, less than 100 mJ / cm 2 and not requiring the obligatory passage by an autocata
• the photosensitive dispersion comprises, in combination, a pigment conferring redox properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymer formulation, a basic compound, an organic solvent and water.
• the pigment is titanium dioxide and is in the form of a fine powder.
• the metal salt is a transition metal salt and in particular chosen from the group comprising copper, gold, platinum, palladium, nickel, cobalt, silver, iron , zinc, cadmium, ruthenium and rhodium, and is preferably copper (II) chloride, copper (II) sulfate, palladium (II) chloride, nickel (II) chloride or a mixture at least two of these salts.
• the liquid film-forming polymer formulation is in the form of a solution or emulsion, and in particular of a solution of the alkyl, acrylic, polyester or epoxy type, of an acrylic emulsion or a mixture of these.
• the present invention also relates to a method of depositing metal on the surface of an insulating substrate, using the photosensitive dispersion, which consists in applying said dispersion in the form of a film to the substrate in a selective manner or not, to dry the film applied to said substrate and to irradiate using ultraviolet and / or laser radiation with a range of wavelengths between 190 and 450 nm and an energy between 25 mJ / cm 2 and 100 mj7cm 2 until a selective or non-selective metal layer is obtained on the substrate.
• the purpose of the photosensitive dispersions with variable viscosity of the invention is to replace the palladium polymer solutions and resins known up to now, the main drawbacks of which have been specified, and to develop dispersions photosensitive with adjustable viscosity and of much wider applicability than known resins, comprising, in combination, a pigment conferring redox properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymer formulation , a basic compound, an organic solvent and water.
• pigment conferring redox properties under light irradiation is understood to mean any pigment capable of forming on the surface a redox system under light irradiation.
• a pigment particle is a semiconductor and when this is subjected to a selected radiation, the energy of these radiations will allow the formation of an oxidoreductive pigment particle. This is how the particle formed from the so will be able to simultaneously carry out the following two reactions, namely the reduction of a cationic species adsorbed on the surface and the oxidation of an ionic species adsorbed on the surface.
• These pigments are used in the form of finely divided powders, generally with a particle size ranging from 10 nanometers to 10 micrometers, advantageously with a particle size of 15 nanometers to 1 micrometer. Titanium dioxide is the most suitable pigment for this purpose.
• the metal of the metal salt is advantageously a transition metal, and is more particularly, copper, gold, platinum, palladium, nickel, cobalt, silver, iron, zinc, cadmium, ruthenium or rhodium or a mixture of at least two of these.
• Particularly advantageous metal salts are copper (II) chloride, copper (II) sulphate, palladium (II) chloride, nickel (II) chloride and mixtures of at least two of these salts.
• liquid film-forming polymer formulation means that the polymer is in the form of a solution or emulsion or of any similar composition and in fact serves as an agent for adjusting the viscosity of the dispersion. photosensitive so as to thus obtain a continuous and homogeneous film on the surface of the substrate using various coating means such as spraying, soaking, application with a roller, screen printing, tempography or the like.
• this polymer also participates in the redox reaction.
• the pigment made semiconductor under light irradiation reduces the metal cations of the metal salt but, for this reaction to be effective, the pigment must also oxidize another compound, a role which is played in the present case by a film.
• the pigment on the one hand reduces the metal cations but on the other hand oxidizes the substrate, for the pigment particles which are in contact with it, thus ensuring good adhesion, as well as the film-forming polymer matrix for the particles which are not in contact with the substrate, thus ensuring a good efficiency of the reaction in “solid” film.
• formulations are film-forming polymer solutions of the alkyl, acrylic, polyester and epoxy type, and acrylic emulsions such as those usually used in the preparation of alkalis, detergents, paints and inks, and mixtures of these. solutions and / or emulsions.
• the complexing agent for metal salt is advantageously of the carboxylic acid, chloride or sulfate type.
• the purpose of this complexing agent, by coordinating with the metal salt, is to dissolve the latter.
• complexing agents of the carboxylic acid type are tartaric acid, citric acid, their derivatives and mixtures of at least two of these compounds.
• the basic compound used in the context of the photosensitive dispersion serves to neutralize all the acids present in the latter and to adjust the pH above 7. Potassium hydroxide, sodium hydroxide, ammonia and their mixtures are examples of usable bases.
• a basic salt such as sodium carbonate, potassium carbonate, calcium carbonate and mixtures thereof. Mixtures of a base and a basic salt are also possible.
• the organic solvent and water have an important role to play in the context of the photosensitive dispersion of the invention.
• the organic solvent will be chosen from ethers, esters, ketones, alcohols, alone or as a mixture.
• the role of organic solvents is manifold. They in particular ensure good adhesion of the film to the insulating substrate and thus good adhesion of the pigment to the substrate, good film formation, rapid drying or even good dispersion of the various components in the catalytic paint.
• the solvents are advantageously used in a mixture so as to measure the property relating to each with respect to their respective role in the product, for the formation of the film or on the substrate.
• solvents used alone or as a mixture are dioxane, cyclohexanone, 2-methoxy-1-methylethyl acetate, mixtures of methyl ether isomers of dipropylene glycol, mixtures of methyl ether isomers dipropylene glycol, and mixtures of at least two of these.
• the water is advantageously deionized water.
• the presence of water in rather small quantities is also important. Indeed, it makes the photosensitive dispersion less corrosive than most formulations of the prior art and allows ease of application in all circumstances by its formulation close to a paint.
• the presence of organic solvent (s) also makes it possible to avoid chemical and / or mechanical pretreatments of the surface of the substrate and better control over the evaporation temperature than in the case of aqueous solutions containing a much higher proportion. significant amount of water.
• wetting agent is a modifying agent of the surface tension and has the aim of reducing the latter by forming an adsorbed layer having a surface tension intermediate between the liquid / liquid or liquid / solid phases.
• interesting wetting agents are silanes, esters of fluoroaliphatic polymers or also products with a high percentage of 2-butoxyethanol. Typical commercial products are Dapro U99 produced by Daniel Product and Schwego-wett (registered trademarks).
• the dispersing agent is advantageously a pigment dispersing agent compatible with acrylic polymers, polyesters and epoxides.
• dispersants are Disperse-AYD W-33 (mixture of nonionic and anionic surfactants in solution in water) and Deuteron ND 953 (aqueous solution of sodium polyaldehyde carbonate) (registered trademarks), respectively produced by the companies Elementis and Deuteron .
• concentrations of the various components of the photosensitive dispersion or catalytic paint of the invention these will of course depend on the nature of these components and on the solvent used.
• the pigment and more particularly titanium dioxide will be used in a concentration, in percentage by weight, of 1 to 50% and preferably of 5 to 25%, the metal salt in a concentration, in percentage by weight, of 0.01 to 5% and preferably of 0.05 to 1%, the complexing agent in a concentration, in percentage by weight, of 0.01 to 10% and preferably of 0 , 1 to 1%, the film-forming polymeric solution and or emulsion in a concentration, in percentage by weight, of 1 to 50% and preferably of 5 to 25%, the base in a concentration, in percentage by weight, of 0, 01 to 5% and preferably 0.1 to 1%, the organic solvent in a concentration, in percentage by weight, from 0.1 to 55% and preferably from 1 to 40% and water in a concentration, in weight percent, from 1 to 15%.
• the concentration of wetting agent, in percentage by weight is from 0.1 to 5% and preferably from 0.25 to 1.0%, and the concentration of dispersing agent, in percentage by weight, is from 0.1 to
• the photosensitive dispersions of the invention are prepared by a simple process of mixing all of the various constituents which it contains.
• the order of addition of each of these constituents is immaterial and has no consequence on the intrinsic properties of the dispersion.
• all the components constituting the photosensitive dispersion are mixed, namely the pigment, the metal salt, the complexing agent, the liquid film-forming polymer formulation, the basic compound, the organic solvent and the water as well as the possible additions and said dispersion is applied in the form of a film to the substrate in a selective manner or not depending on the intended application.
• the film applied to the substrate is dried and irradiated using ultraviolet and / or laser radiation with a range of wavelengths between 190 and 450 nm and an energy between 25 mJ / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.
• Palladium catalytic paint for the selective metallization or not of a polymeric substrate Palladium catalytic paint for the selective metallization or not of a polymeric substrate.
• Dispersing agent manufactured by Elementis mixture of nonionic and anionic surfactants in water.
• the paint or catalytic dispersion is applied to a polymeric substrate, without any pretreatment of the latter, by soaking, spraying, application with a roller or pad printing and is then air dried for a few seconds.
• the film thus obtained is irradiated using commonly used UV lamps and / or laser and having a spectrum between 250 and 450 nm, the time necessary for the film to receive a minimum energy of 25 mJ / cm 2 . If selective metallization is desired, this irradiation will be done through a mask. This results in the deposition of a layer of selective or non-selective catalytic palladium. In the case of selective metallization, the non-irradiated parts are dissolved in water. A metal overload by electroplating is then made possible, the substrate being made conductive.
• Example 2 Copper catalytic paint for the selective metallization or not of a polymeric substrate.
• Dispersing agent manufactured by Elementis mixture of nonionic and anionic surfactants in water.
• Film-forming acrylic polymer emulsion manufactured by the company Johnson Polymer, registered trademark.
• Wetting agent manufactured by the Daniel Product company silicone-free interfacial tension modifier.
• Example 1 The procedure is as in Example 1. This results in the deposition of a layer of selective or non-selective catalytic palladium. In the case of selective metallization, the non-irradiated parts are dissolved in water. A metal overload by electroplating is then made possible.
• the metal salt could be replaced in the concentrations indicated by all the salts specifically mentioned, namely copper (II) sulphate and palladium and nickel (II) chlorides.
• the substrates tested in the context of the above examples are common plastics such as ABS, ABS-PC (polycarbonate), certain polyamides, epoxy materials, polycarbonates and the like.
• the dispersion of the invention is a formulation extremely close to a paint making it easily applicable in all circumstances.
• the photosensitive catalytic dispersion or paint of the invention does not exhibit any corrosivity unlike the formulations of the prior art which are all very corrosive.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Electrochemistry (AREA)
• Health & Medical Sciences (AREA)
• Toxicology (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Paints Or Removers (AREA)
• Chemically Coating (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Colloid Chemistry (AREA)
• Materials For Photolithography (AREA)
• Insulated Metal Substrates For Printed Circuits (AREA)
• Formation Of Insulating Films (AREA)
• Silicon Compounds (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Conductive Materials (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Catalysts (AREA)
• Electroplating Methods And Accessories (AREA)
• Parts Printed On Printed Circuit Boards (AREA)

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• 2003
  • 2003-01-03 BE BE2003/0007A patent/BE1015271A3/fr not_active IP Right Cessation
  • 2003-12-24 US US10/541,210 patent/US20060122297A1/en not_active Abandoned
  • 2003-12-24 AU AU2003289778A patent/AU2003289778B2/en not_active Ceased
  • 2003-12-24 DE DE60305213T patent/DE60305213T2/de not_active Expired - Lifetime
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  • 2003-12-24 ES ES03782026T patent/ES2261991T3/es not_active Expired - Lifetime
  • 2003-12-24 PT PT03782026T patent/PT1587967E/pt unknown
  • 2003-12-24 BR BRPI0317897-8A patent/BR0317897B1/pt not_active IP Right Cessation
  • 2003-12-24 WO PCT/BE2003/000229 patent/WO2004061157A1/fr active IP Right Grant
  • 2003-12-24 KR KR1020057012582A patent/KR100777033B1/ko not_active IP Right Cessation
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  • 2003-12-24 CA CA2512202A patent/CA2512202C/fr not_active Expired - Fee Related
  • 2003-12-24 EP EP03782026A patent/EP1587967B1/de not_active Expired - Lifetime
  • 2003-12-24 CN CN200380108171A patent/CN100587110C/zh not_active Expired - Fee Related
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• 2005
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• 2008
  • 2008-08-20 US US12/222,965 patent/US7731786B2/en not_active Expired - Fee Related

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