EP1587967B1 - Photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate and use of same - Google Patents

Photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate and use of same Download PDF

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Publication number
EP1587967B1
EP1587967B1 EP03782026A EP03782026A EP1587967B1 EP 1587967 B1 EP1587967 B1 EP 1587967B1 EP 03782026 A EP03782026 A EP 03782026A EP 03782026 A EP03782026 A EP 03782026A EP 1587967 B1 EP1587967 B1 EP 1587967B1
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Prior art keywords
dispersion according
dispersion
concentration
percentage
weight
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German (de)
French (fr)
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EP1587967A1 (en
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Olivier Dupuis
Mary-Helene Delvaux
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Semika SA
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Semika SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—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 an adjustable viscosity photosensitive dispersion for metal deposition on an insulating substrate and to its use.
  • Patent EP 0 687 311 of the applicant relates to a polymer resin with viscosity and pH adjustable 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 hydroxyl and / or carboxyl groups which are soluble in water, a basic compound and a solvent chosen from water, methanol and ethanol, the pH value being between 1 and 10, as well as its applications for depositing catalytic palladium on the substrate surface and for metallizing these surfaces.
  • An essential object of the present invention is, therefore, to overcome the aforementioned drawbacks and to present a photosensitive dispersion with adjustable viscosity no longer requiring the use of a noble metal such as palladium and also using other metals more common and less expensive and whose photosensitivity is widened 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 does not require the compulsory passage through an autocatalytic bath for the metallization of the substrate, thus allowing direct electrolytic metallization.
  • a noble metal such as palladium
  • other metals more common and less expensive
  • photosensitivity is widened 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 does not require the compulsory passage through an autocatalytic bath for the metallization of
  • the photosensitive dispersion comprises, in combination, a pigment conferring oxidation-reduction properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymeric 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 and 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 comprises applying said dispersion in the form of a film to the substrate in a selective manner. or not, drying the applied film on said substrate and irradiating with ultraviolet and / or laser radiation of a wavelength range of between 190 and 450 nm and an energy of between 25 and 450 nm. mJ / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.
  • variable viscosity-sensitive photosensitive dispersions of the invention is to replace the palladium polymer solutions and resins known hitherto, the main disadvantages of which have been specified, and to develop dispersions.
  • photosensitive material with adjustable viscosity and a much wider applicability than known resins comprising, in combination, a pigment conferring oxidation-reduction properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymeric formulation , a basic compound, an organic solvent and water.
  • pigment conferring oxidation-reduction properties under light irradiation means any pigment capable of forming on the surface an oxidoreductive system under light irradiation.
  • a pigment particle is a semiconductor and when it is subjected to a chosen radiation, the energy of these radiations will allow the formation of an oxidation-reduction pigment particle. This is how the particle formed from the The two following reactions, namely the reduction of a cationic species adsorbed on the surface and the oxidation of an ionic species adsorbed on the surface, can be carried out simultaneously.
  • These pigments are used in the form of finely divided powders, generally of a particle size ranging from 10 nanometers to 10 microns, advantageously of 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 thereof.
  • Particularly preferred 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 is understood to mean that the polymer is in the form of a solution or emulsion or of any analogous composition and serves in fact as a control agent for the viscosity of the dispersion. photosensitive so as to obtain a continuous and homogeneous film on the surface of the substrate using different coating means such as spraying, dipping, roller application, screen printing, tempography or the like.
  • this polymer also participates in the oxidation-reduction reaction.
  • the pigment rendered semiconductor under the 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 held in this case by a film solid from which all the solvents were evaporated during the drying after coating. Therefore, the pigment on the one hand reduces the metal cations but on the other hand oxidizes the substrate, for the pigment particles that are in contact with it, thus ensuring good adhesion, as well as the film-forming polymer matrix for particles that are not in contact with the substrate, thus ensuring a good efficiency of the "solid" film reaction.
  • formulations are film-forming polymeric 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 thereof. solutions and / or emulsions.
  • the complexing agent for metal salt is advantageously of the carboxylic acid, chloride or sulfate type. This complexing agent, by coordinating with the metal salt, is intended to solubilize it.
  • carboxylic acid type complexing agents 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 it and to adjust the pH above 7.
  • Potassium hydroxide, sodium hydroxide, ammonia and their mixtures are examples of usable bases. It is also possible to envisage the use of 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 multiple. They ensure in particular a good adhesion of the film on the insulating substrate and thus a good adhesion of the pigment on the substrate, good film formation, fast drying or good dispersion of the various components in the catalytic paint.
  • the solvents are advantageously used in a mixture so as to measure the property relative to each one with respect to their respective roles in the product, for the formation of the film or on the substrate.
  • solvents used alone or in a mixture are dioxane, cyclohexanone, 2-methoxy-1-methylethyl acetate, mixtures of isomers of dipropylene glycol methyl ether, mixtures of isomers of methyl ether dipropylene glycol, and mixtures of at least two thereof.
  • the water is advantageously deionized water.
  • the presence of water in a rather small quantity 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 substrate surface and better control of the evaporation temperature than in the case of aqueous solutions containing a much higher proportion significant amount of water.
  • wetting agent is a surface tension modifier and is intended to reduce it by forming an adsorbed layer having an intermediate surface tension between the liquid / liquid or liquid / solid phases.
  • Wetting agents of interest are silanes, fluoroaliphatic polymer esters or products with a high percentage of 2-butoxyethanol. Typical commercial products are Dapro U99 manufactured by Daniel Product and Schwego-wett (registered trademarks).
  • the dispersing agent is advantageously a pigment dispersant compatible with acrylic polymers, polyesters and epoxides.
  • dispersing agents are Disperse-AYD W-33 (mixture of nonionic surfactants and anionic surfactants in solution in water) and Deuteron ND 953 (aqueous solution of sodium polyaldehyde carbonate) (registered trademarks), respectively manufactured by Elementis and Deuteron companies .
  • concentrations of the various components of the photosensitive dispersion or catalytic paint of the invention will of course depend on the nature of these components and the solvent used.
  • the pigment, and more particularly the titanium dioxide, in a concentration in weight percentage, of from 1 to 50% and preferably from 5 to 25% by weight, the metal salt will generally be used.
  • the complexing agent 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 to 1 to 1%, the solution and / or film-forming polymeric emulsion in a concentration, in weight percentage, of 1 to 50% and preferably 5 to 25%, the base in a concentration, in percentage by weight, of 0 , From 0.1 to 5% and preferably from 0.1 to 1%, the organic solvent in a concentration, in percentage by weight, of 0.1 to 55% and preferably of 1 to 40% and the water in a concentration of in percent by weight, from 1 to 15%.
  • the wetting agent concentration, in weight percent is from 0.1 to 5% and preferably from 0.25 to 1.0%, and the dispersant concentration, in weight percent, is from 0.1 to 5% by weight. 15% and preferably 0.2 to 2%.
  • the preparation of the photosensitive dispersions of the invention is carried out in a simple process of mixing all the different constituents that it contains.
  • the order of addition of each of these constituents is unimportant 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 applies said dispersion in the form of a film on the substrate in a selective manner or not depending on the intended application.
  • the applied film is dried on the substrate and irradiated with ultraviolet and / or laser radiation of a wavelength range between 190 and 450 nm and an energy of between 25 mJ. / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.
  • Catalytic palladium paint for the selective metallization or otherwise of a polymeric substrate.
  • Composition of the dispersion Concentration in% by weight Finely divided titanium dioxide powder 5 to 25 dioxane 10 to 30 2-methoxy-1-methylethyl acetate 25 to 40 Mixture of dipropylene glycol methyl ether isomers 1 to 15 Disperse-AYD® W33 1) 0.2 to 2 Joncryl® 537 2) 5 to 25 Mixture of tripropylene glycol methyl ether isomers 1 to 5 Dapro® U99 3) 0.25 to 1 Palladium (II) chloride (metal salt) 0.05 to 1 Tartaric acid (complexing agent) 0.1 to 1 Ammonia (base) 0.1 to 1 Deionized water 1 to 15 1) Dispersing agent manufactured by Elementis: a mixture of nonionic and anionic surfactants in water. 2) polymeric acrylic film-forming emulsion, manufactured by the company Johnson Polymer, registered trademark. 3) Wetting agent manufactured by Daniel Product:
  • the catalytic paint or dispersion is applied to a polymeric substrate, without any pretreatment of the latter, by soaking, spraying, roller coating or pad printing and is then air-dried for a few seconds.
  • the film thus obtained is irradiated with UV lamps commonly used and / or laser and having a spectrum between 250 and 450 nm, the time required for the film to receive a minimum energy of 25 mJ / cm 2 . If a selective metallization is desired, this irradiation will be done through a mask. This results in the deposition of a selective catalytic palladium layer or not. In the case of selective metallization, the non-irradiated parts are solubilized in water. A metal overload by electroplating is then made possible, the substrate being made conductive.
  • Copper catalytic paint for the selective metallization or not of a polymeric substrate.
  • Composition of the dispersion Concentration in% by weight Finely divided titanium dioxide powder 5 to 25 dioxane 10 to 30 2-methoxy-1-methylethyl acetate 25 to 40 Mixture of dipropylene glycol methyl ether isomers 1 to 15 Disperse-AYD® W33 1) 0.2 to 2 Joncry® 537 2) 5 to 25 Mixture of tripropylene glycol methyl ether isomers 1 to 5 Dapro® U99 3) 0.25 to 1 Palladium (II) chloride (metal salt) 0.05 to 1 Citric acid (complexing) 0.1 to 1 Ammonia (base) 0.1 to 1 Deionized water 1 to 15 1) Dispersing agent manufactured by Elementis: a mixture of nonionic and anionic surfactants in water. 2) polymeric acrylic film-forming emulsion, manufactured by the company Johnson Polymer, registered trademark. 3) Wetting agent manufactured by Daniel Product: interfacial
  • Example 1 The procedure is as in Example 1. This results in the deposition of a selective catalytic palladium layer or not. In the case of selective metallization, the non-irradiated parts are solubilized in water. A metal overload by electroplating is then made possible.
  • the metal salt could be replaced in the concentrations indicated by all the specifically mentioned salts, namely copper (II) sulphate and palladium and nickel (II) chlorides.
  • the substrates tested in the context of the abovementioned 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 dispersion or catalytic photosensitive paint of the invention has no corrosivity in contrast to the formulations of the prior art which are all very corrosive.

Abstract

The invention relates to a photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate, which combines the following: a pigment providing oxidation-reduction properties under light irradiation, a metallic salt, a complex-forming agent for the metallic salt, a liquid film-forming polymer formulation, a basic compound, an organic solvent and water. The invention also relates to the use of said dispersion.

Description

La présente invention est relative à une dispersion photosensible à viscosité ajustable pour le dépôt de métal sur un substrat isolant et à son utilisation.The present invention relates to an adjustable viscosity photosensitive dispersion for metal deposition on an insulating substrate and to its use.

Le brevet EP 0 687 311 de la déposante concerne une résine polymérique à viscosité et pH ajustables pour le dépôt de palladium catalytique sur un substrat, comprenant, en combinaison, un sel de palladium, un complexant du type acide carboxylique ou chlorure, un polymère contenant des groupes hydroxyle et/ou carboxyle soluble dans l'eau, un composé basique et un solvant choisi parmi l'eau, le méthanol et l'éthanol, la valeur de pH étant comprise entre 1 et 10, ainsi qu'à ses applications pour le dépôt de palladium catalytique sur la surface de substrat et pour la métallisation de ces surfaces. Bien que ce type de résine polymérique au palladium se soit révélée avantageuse dans un grand nombre d'applications de métallisation de substrats polymériques et autres, notamment en raison de sa stabilité dans le temps et de l'ajustabilité de ses viscosité et pH, elle présente cependant un certain nombre d'inconvénients, parmi lesquels, l'utilisation obligatoire de palladium qui est un métal noble à la fois coûteux et extrêmement fluctuable sur le marché et le passage obligatoire par un bain autocatalytique (electroless) pour la métallisation du substrat non conducteur et également en raison du fait que la photosensibilité de la résine est réduite à une gamme de longueurs d'onde étroite comprises entre 190 et 300 nm, limitant ainsi fortement le type d'applications envisageables et la source de rayonnement utilisable à cet égard.Patent EP 0 687 311 of the applicant relates to a polymer resin with viscosity and pH adjustable 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 hydroxyl and / or carboxyl groups which are soluble in water, a basic compound and a solvent chosen from water, methanol and ethanol, the pH value being between 1 and 10, as well as its applications for depositing catalytic palladium on the substrate surface and for metallizing these surfaces. Although this type of polymeric palladium resin has proved advantageous in a large number of metallization applications of polymeric and other substrates, particularly because of its stability over time and the adjustability of its viscosity and pH, it presents However, there are a number of disadvantages, including the obligatory use of palladium, which is a noble metal that is both expensive and extremely fluctuating on the market, and the obligatory passage through an electroless bath for the metallization of the non-conductive substrate. and also because the photosensitivity of the resin is reduced to a range of narrow wavelengths between 190 and 300 nm, thus greatly limiting the type of applications that can be envisaged and the radiation source that can be used in this regard.

Un des buts essentiels de la présente invention consiste, par conséquent, à remédier aux inconvénients précités et à présenter une dispersion photosensible à viscosité ajustable ne nécessitant plus obligatoirement l'utilisation d'un métal noble tel que le palladium et faisant appel également à d'autres métaux plus communs et moins coûteux et dont la photosensibilité est élargie à une gamme de longueurs d'onde entre 190 et 450 nm et demandant une énergie d'irradiation beaucoup plus faible que les résines polymériques connues jusqu'ici, inférieure à 100 mJ/cm2 et ne nécessitant pas le passage obligatoire par un bain autocatalytique pour la métallisation du substrat, permettant dès lors une métallisation électrolytique directe.An essential object of the present invention is, therefore, to overcome the aforementioned drawbacks and to present a photosensitive dispersion with adjustable viscosity no longer requiring the use of a noble metal such as palladium and also using other metals more common and less expensive and whose photosensitivity is widened 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 does not require the compulsory passage through an autocatalytic bath for the metallization of the substrate, thus allowing direct electrolytic metallization.

A cet effet, suivant l'invention, la dispersion photosensible comprend, en combinaison, un pigment conférant des propriétés d'oxydoréduction sous irradiation lumineuse, un sel métallique, un complexant pour le sel métallique, une formulation polymérique filmogène liquide, un composé basique, un solvant organique et de l'eau.For this purpose, according to the invention, the photosensitive dispersion comprises, in combination, a pigment conferring oxidation-reduction properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymeric formulation, a basic compound, an organic solvent and water.

Suivant une forme de réalisation avantageuse de l'invention, le pigment est du dioxyde de titane et est sous la forme d'une fine poudre.According to an advantageous embodiment of the invention, the pigment is titanium dioxide and is in the form of a fine powder.

Suivant une autre forme de réalisation avantageuse, le sel métallique est un sel de métal de transition et notamment choisi dans le groupe comprenant le cuivre, l'or, le platine, le palladium, le nickel, le cobalt, l'argent, le fer, le zinc, le cadmium, le ruthénium et le rhodium, et est préférentiellement le chlorure de cuivre (II), le sulfate de cuivre (II), le chlorure de palladium (II), le chlorure de nickel (II) ou un mélange d'au moins deux de ces sels.According to another advantageous embodiment, the metal salt is a transition metal salt and in particular chosen from the group comprising copper, gold, platinum, palladium, nickel, cobalt, silver and 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.

Suivant encore une autre forme de réalisation avantageuse de l'invention, la formulation polymérique filmogène liquide est sous la forme d'une solution ou émulsion, et notamment d'une solution du type alkyle, acrylique, polyester ou époxy, d'une émulsion acrylique ou d'un mélange de celles-ci.According to yet another advantageous embodiment of the invention, 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.

La présente invention concerne également un procédé de dépôt de métal sur la surface d'un substrat isolant, à l'aide de la dispersion photosensible, qui consiste à appliquer ladite dispersion sous la forme d'un film sur le substrat d'une manière sélective ou non, à sécher le film appliqué sur ledit substrat et à irradier à l'aide d'un rayonnement ultraviolet et/ou laser d'une gamme de longueurs d'onde comprises entre 190 et 450 nm et d'une énergie comprise entre 25 mJ/cm2 et 100 mJ/cm2 jusqu'à l'obtention d'une couche de métal sélective ou non sur le substrat.The present invention also relates to a method of depositing metal on the surface of an insulating substrate, using the photosensitive dispersion, which comprises applying said dispersion in the form of a film to the substrate in a selective manner. or not, drying the applied film on said substrate and irradiating with ultraviolet and / or laser radiation of a wavelength range of between 190 and 450 nm and an energy of between 25 and 450 nm. mJ / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.

D'autres détails et particularités de l'invention ressortiront de la description ci-après, à titre d'exemple non limitatif, de dispersions photosensibles suivant l'invention et de leurs applications pour le dépôt de métal sur la surface de substrat isolant ainsi que pour la métallisation de ces surfaces.Other details and particularities of the invention will emerge from the following description, by way of non-limiting example, of photosensitive dispersions according to the invention and of their applications for the deposition of metal on the surface of insulating substrate as well as for the metallization of these surfaces.

Comme on l'a déjà précisé précédemment, le but des dispersions photosensibles à viscosité variable de l'invention est de remplacer les solutions et résines polymériques au palladium connues jusqu'à présent, dont les inconvénients principaux ont été précisés, et de développer des dispersions photosensibles à viscosité ajustable et d'une applicabilité beaucoup plus étendue que les résines connues, comprenant, en combinaison, un pigment conférant des propriétés d'oxydoréduction sous irradiation lumineuse, un sel métallique, un complexant pour le sel métallique, une formulation polymérique filmogène liquide, un composé basique, un solvant organique et de l'eau.As already mentioned above, the purpose of the variable viscosity-sensitive photosensitive dispersions of the invention is to replace the palladium polymer solutions and resins known hitherto, the main disadvantages of which have been specified, and to develop dispersions. photosensitive material with adjustable viscosity and a much wider applicability than known resins, comprising, in combination, a pigment conferring oxidation-reduction properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymeric formulation , a basic compound, an organic solvent and water.

On entend par l'expression "pigment conférant des propriétés d'oxydoréduction sous irradiation lumineuse" tout pigment capable de former en surface un système oxydoréducteur sous irradiation lumineuse. En fait, une particule de pigment est un semi-conducteur et lorsque celle-ci est soumise à un rayonnement choisi, l'énergie de ces rayonnements va permettre la formation d'une particule pigmentaire oxydoréductrice. C'est ainsi que la particule formée de la sorte va pouvoir effectuer simultanément les deux réactions suivantes, à savoir la réduction d'une espèce cationique adsorbée en surface et l'oxydation d'une espèce ionique adsorbée en surface. Ces pigments sont utilisés sous la forme de poudres finement divisées, généralement d'une taille de particule allant de 10 nanomètres à 10 micromètres, avantageusement d'une taille de particule de 15 nanomètres à 1 micromètre. Le dioxyde de titane est le pigment convenant le mieux à cet effet.The expression "pigment conferring oxidation-reduction properties under light irradiation" means any pigment capable of forming on the surface an oxidoreductive system under light irradiation. In fact, a pigment particle is a semiconductor and when it is subjected to a chosen radiation, the energy of these radiations will allow the formation of an oxidation-reduction pigment particle. This is how the particle formed from the The two following reactions, namely the reduction of a cationic species adsorbed on the surface and the oxidation of an ionic species adsorbed on the surface, can be carried out simultaneously. These pigments are used in the form of finely divided powders, generally of a particle size ranging from 10 nanometers to 10 microns, advantageously of a particle size of 15 nanometers to 1 micrometer. Titanium dioxide is the most suitable pigment for this purpose.

Le métal du sel métallique est avantageusement un métal de transition, et est plus particulièrement, le cuivre, l'or, le platine, le palladium, le nickel, le cobalt, l'argent, le fer, le zinc, le cadmium, le ruthénium ou le rhodium ou un mélange d'au moins deux de ceux-ci. Des sels métalliques particulièrement avantageux sont le chlorure de cuivre (II), le sulfate de cuivre (II), le chlorure de palladium (II), le chlorure de nickel (II) et les mélanges d'au moins deux de ces sels.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 thereof. Particularly preferred metal salts are copper (II) chloride, copper (II) sulphate, palladium (II) chloride, nickel (II) chloride and mixtures of at least two of these salts.

Suivant l'invention, on entend par l'expression "formulation polymérique filmogène liquide" que le polymère est sous la forme d'une solution ou émulsion ou de toute composition analogue et sert en fait d'agent de réglage de la viscosité de la dispersion photosensible de manière à obtenir ainsi un film continu et homogène à la surface du substrat à l'aide de différents moyens d'enduction tels que pulvérisation, trempage, application au rouleau, sérigraphie, tempographie ou analogue. De plus, ce polymère participe également à la réaction d'oxydoréduction. En fait, le pigment rendu semi-conducteur sous l'irradiation lumineuse réduit les cations métalliques du sel métallique mais, pour que cette réaction soit efficace, le pigment doit également oxyder un autre composé, rôle qui est tenu dans le cas présent par un film solide duquel tous les solvants ont été évaporés lors du séchage après enduction. Dès lors, le pigment d'une part réduit les cations métalliques mais d'autre part oxyde le substrat, pour les particules de pigment qui sont en contact avec celui-ci, assurant ainsi une bonne adhérence, ainsi que la matrice polymérique filmogène pour les particules qui ne sont pas en contact avec le substrat, assurant ainsi une bonne efficacité de la réaction en film "solide". Des exemples de formulations sont les solutions polymériques filmogènes du type alkyle, acrylique, polyester et époxy, et les émulsions acryliques telles que celles habituellement utilisées dans la préparation d'alcalins, de détergents, de peintures et d'encres, et les mélanges de ces solutions et/ou émulsions.According to the invention, the expression "liquid film-forming polymer formulation" is understood to mean that the polymer is in the form of a solution or emulsion or of any analogous composition and serves in fact as a control agent for the viscosity of the dispersion. photosensitive so as to obtain a continuous and homogeneous film on the surface of the substrate using different coating means such as spraying, dipping, roller application, screen printing, tempography or the like. In addition, this polymer also participates in the oxidation-reduction reaction. In fact, the pigment rendered semiconductor under the 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 held in this case by a film solid from which all the solvents were evaporated during the drying after coating. Therefore, the pigment on the one hand reduces the metal cations but on the other hand oxidizes the substrate, for the pigment particles that are in contact with it, thus ensuring good adhesion, as well as the film-forming polymer matrix for particles that are not in contact with the substrate, thus ensuring a good efficiency of the "solid" film reaction. Examples of formulations are film-forming polymeric 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 thereof. solutions and / or emulsions.

Le complexant pour sel métallique est avantageusement du type acide carboxylique, chlorure ou sulfate. Ce complexant, en se coordinant au sel métallique, a pour but de solubiliser celui-ci. Des exemples de complexants du type acide carboxylique sont l'acide tartrique, l'acide citrique, leurs dérivés et les mélanges d'au moins deux de ces composés.The complexing agent for metal salt is advantageously of the carboxylic acid, chloride or sulfate type. This complexing agent, by coordinating with the metal salt, is intended to solubilize it. Examples of carboxylic acid type complexing agents are tartaric acid, citric acid, their derivatives and mixtures of at least two of these compounds.

Le composé basique utilisé dans le cadre de la dispersion photosensible sert à neutraliser tous les acides présents dans celle-ci et à régler le pH au-delà de 7. L'hydroxyde de potassium, l'hydroxyde de sodium, l'ammoniaque et leurs mélanges sont des exemples de bases utilisables. On pourrait également envisager l'utilisation d'un sel basique tel que le carbonate de sodium, le carbonate de potassium, le carbonate de calcium et leurs mélanges. Des mélanges d'une base et d'un sel basique sont également envisageables.The basic compound used in the context of the photosensitive dispersion serves to neutralize all the acids present in it and to adjust the pH above 7. Potassium hydroxide, sodium hydroxide, ammonia and their mixtures are examples of usable bases. It is also possible to envisage the use of 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.

Le solvant organique et l'eau ont un rôle important à jouer dans le cadre de la dispersion photosensible de l'invention. Le solvant organique sera choisi parmi les éthers, esters, cétones, alcools, seuls ou en mélange. Le rôle des solvants organique est multiple. Ils assurent notamment une bonne adhérence du film sur le substrat isolant et ainsi un bon accrochage du pigment sur le substrat, une bonne formation des films, un séchage rapide ou encore une bonne dispersion des différents composants dans la peinture catalytique. Les solvants sont avantageusement utilisés en mélange de manière à doser la propriété relative à chacun vis-à-vis de leur rôle respectif dans le produit, pour la formation du film ou sur le substrat. Des exemples de solvants utilisés isolément ou en mélange sont le dioxanne, la cyclohexanone, l'acétate de 2-méthoxy-1-méthyléthyle, les mélanges d'isomères d'éther méthylique de dipropylène glycol, les mélanges d'isomères d'éther méthylique de dipropylène glycol, et les mélanges d'au moins deux de ceux-ci. L'eau est avantageusement de l'eau désionisée. La présence de l'eau en quantité plutôt faible est également importante. En effet, celle-ci rend la dispersion photosensible moins corrosive que la plupart des formulations de la technique antérieure et permet une facilité d'application en toutes circonstances par sa formulation proche d'une peinture. La présence de solvant(s) organique(s) permet également d'éviter les prétraitements chimiques et/ou mécaniques de la surface du substrat et un meilleur contrôle sur la température d'évaporation que dans le cas des solutions aqueuses contenant une proportion beaucoup plus importante d'eau.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 multiple. They ensure in particular a good adhesion of the film on the insulating substrate and thus a good adhesion of the pigment on the substrate, good film formation, fast drying or good dispersion of the various components in the catalytic paint. The solvents are advantageously used in a mixture so as to measure the property relative to each one with respect to their respective roles in the product, for the formation of the film or on the substrate. Examples of solvents used alone or in a mixture are dioxane, cyclohexanone, 2-methoxy-1-methylethyl acetate, mixtures of isomers of dipropylene glycol methyl ether, mixtures of isomers of methyl ether dipropylene glycol, and mixtures of at least two thereof. The water is advantageously deionized water. The presence of water in a rather small quantity 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 substrate surface and better control of the evaporation temperature than in the case of aqueous solutions containing a much higher proportion significant amount of water.

Comme ajouts compatibles avec la dispersion photosensible de l'invention, on ajoutera avantageusement ainsi qu'on l'a déjà précisé précédemment, un ou des mélanges d'agents mouillant et/ou dispersant. L'agent mouillant est un agent modificateur de la tension de surface et a pour but de réduire celle-ci en formant une couche adsorbée ayant une tension de surface intermédiaire entre les phases liquide/liquide ou liquide/solide. Des agents mouillants intéressants sont les silanes, les esters de polymères fluoroaliphatiques ou encore les produits à haut pourcentage en 2-butoxyéthanol. Des produits du commerce typiques sont le Dapro U99 fabriqué par la société Daniel Product et le Schwego-wett (marques déposées). L'agent dispersant est avantageusement un dispersant pour pigment compatible avec les polymères acryliques, polyesters et époxydes. Il améliore la dispersion des particules solides de pigment pouvant être présentes dans la peinture catalytique. Des exemples d'agents dispersants sont le Disperse-AYD W-33 (mélange d'agents tensioactifs non ionique et anionique en solution dans de l'eau) et le Deuteron ND 953 (solution aqueuse de polyaldéhydocarbonate de sodium) (marques déposées), respectivement fabriqués par les sociétés Elementis et Deuteron.As additions compatible with the photosensitive dispersion of the invention, one or more mixtures of wetting and / or dispersing agents will advantageously be added as has already been mentioned previously. The wetting agent is a surface tension modifier and is intended to reduce it by forming an adsorbed layer having an intermediate surface tension between the liquid / liquid or liquid / solid phases. Wetting agents of interest are silanes, fluoroaliphatic polymer esters or products with a high percentage of 2-butoxyethanol. Typical commercial products are Dapro U99 manufactured by Daniel Product and Schwego-wett (registered trademarks). The dispersing agent is advantageously a pigment dispersant compatible with acrylic polymers, polyesters and epoxides. It improves the dispersion of the solid particles of pigment that may be present in the catalytic paint. Examples of dispersing agents are Disperse-AYD W-33 (mixture of nonionic surfactants and anionic surfactants in solution in water) and Deuteron ND 953 (aqueous solution of sodium polyaldehyde carbonate) (registered trademarks), respectively manufactured by Elementis and Deuteron companies .

En ce qui concerne les concentrations des différents composants de la dispersion photosensible ou peinture catalytique de l'invention, celles-ci dépendront bien entendu de la nature de ces composants et du solvant utilisé. Toutefois, on utilisera d'une manière générale, suivant l'invention, le pigment et plus particulièrement le dioxyde de titane en une concentration, en pourcentage en poids, de 1 à 50 % et de préférence de 5 à 25 %, le sel métallique en une concentration, en pourcentage en poids, de 0,01 à 5 % et de préférence de 0,05 à 1 %, le complexant en une concentration, en pourcentage en poids, de 0,01 à 10 % et de préférence de 0,1 à 1 %, la solution et/ou émulsion polymérique filmogène en une concentration, en pourcentage en poids, de 1 à 50 % et de préférence de 5 à 25 %, la base en une concentration, en pourcentage en poids, de 0,01 à 5 % et de préférence de 0,1 à 1 %, le solvant organique en une concentration, en pourcentage en poids, de 0,1 à 55 % et de préférence de 1 à 40 % et l'eau en une concentration, en pourcentage en poids, de 1 à 15 %. La concentration en agent mouillant, en pourcentage en poids, est de 0,1 à 5 % et de préférence de 0,25 à 1,0 %, et la concentration en agent dispersant, en pourcentage en poids, est de 0,1 à 15 % et de préférence de 0,2 à 2 %.As regards the 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 the solvent used. However, according to the invention, the pigment, and more particularly the titanium dioxide, in a concentration in weight percentage, of from 1 to 50% and preferably from 5 to 25% by weight, the metal salt, will generally be used. 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 to 1 to 1%, the solution and / or film-forming polymeric emulsion in a concentration, in weight percentage, of 1 to 50% and preferably 5 to 25%, the base in a concentration, in percentage by weight, of 0 , From 0.1 to 5% and preferably from 0.1 to 1%, the organic solvent in a concentration, in percentage by weight, of 0.1 to 55% and preferably of 1 to 40% and the water in a concentration of in percent by weight, from 1 to 15%. The wetting agent concentration, in weight percent, is from 0.1 to 5% and preferably from 0.25 to 1.0%, and the dispersant concentration, in weight percent, is from 0.1 to 5% by weight. 15% and preferably 0.2 to 2%.

La préparation des dispersions photosensibles de l'invention se fait suivant un simple processus de mélange de la totalité des différents constituants qu'elle contient. L'ordre d'addition de chacun de ces constituants est sans importance et n'a pas de conséquence sur les propriétés intrinsèques de la dispersion. En fait, on mélange tous les composants constituant la dispersion photosensible, à savoir le pigment, le sel métallique, le complexant, la formulation polymérique filmogène liquide, le composé basique, le solvant organique et l'eau ainsi que les éventuels ajouts et on applique ladite dispersion sous la forme d'un film sur le substrat d'une manière sélective ou non en fonction de l'application envisagée. Ensuite, on sèche le film appliqué sur le substrat et on irradie à l'aide d'un rayonnement ultraviolet et/ou laser d'une gamme de longueurs d'onde comprises entre 190 et 450 nm et d'une énergie comprise entre 25 mJ/cm2 et 100 mJ/cm2 jusqu'à l'obtention d'une couche de métal sélective ou non sur le substrat.The preparation of the photosensitive dispersions of the invention is carried out in a simple process of mixing all the different constituents that it contains. The order of addition of each of these constituents is unimportant and has no consequence on the intrinsic properties of the dispersion. In fact, 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 applies said dispersion in the form of a film on the substrate in a selective manner or not depending on the intended application. Then, the applied film is dried on the substrate and irradiated with ultraviolet and / or laser radiation of a wavelength range between 190 and 450 nm and an energy of between 25 mJ. / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.

On donne ci-après des exemples de dispersions photosensibles de l'invention ainsi que leurs techniques de mise en oeuvre.The following are examples of photosensitive dispersions of the invention as well as their techniques of implementation.

Exemple 1Example 1

Peinture catalytique au palladium pour la métallisation sélective ou non d'un substrat polymérique. Composition de la dispersion Concentration en % en poids Dioxyde de titane en poudre finement divisée 5 à 25 Dioxanne 10 à 30 Acétate de 2-méthoxy-1-méthyléthyle 25 à 40 Mélange d'isomères d'éther méthylique de dipropylène glycol 1 à 15 Disperse-AYD® W33 1) 0,2 à 2 Joncryl® 537 2) 5 à 25 Mélange d'isomères d'éther méthylique de tripropylène glycol 1 à 5 Dapro® U99 3) 0,25 à 1 Chlorure de palladium (II) (sel métallique) 0,05 à 1 Acide tartrique (complexant) 0,1 à 1 Ammoniaque (base) 0,1 à 1 Eau désionisée 1 à 15 1) Agent dispersant fabriqué par la société Elementis : mélange d'agents tensioactifs non ionique et anionique dans de l'eau. 2) Emulsion polymérique acrylique filmogène, fabriquée par la société Johnson Polymer, marque déposée. 3) Agent mouillant fabriqué par la société Daniel Product : modificateur de tension interfaciale sans silicone. Catalytic palladium paint for the selective metallization or otherwise of a polymeric substrate. Composition of the dispersion Concentration in% by weight Finely divided titanium dioxide powder 5 to 25 dioxane 10 to 30 2-methoxy-1-methylethyl acetate 25 to 40 Mixture of dipropylene glycol methyl ether isomers 1 to 15 Disperse-AYD® W33 1) 0.2 to 2 Joncryl® 537 2) 5 to 25 Mixture of tripropylene glycol methyl ether isomers 1 to 5 Dapro® U99 3) 0.25 to 1 Palladium (II) chloride (metal salt) 0.05 to 1 Tartaric acid (complexing agent) 0.1 to 1 Ammonia (base) 0.1 to 1 Deionized water 1 to 15 1) Dispersing agent manufactured by Elementis: a mixture of nonionic and anionic surfactants in water. 2) polymeric acrylic film-forming emulsion, manufactured by the company Johnson Polymer, registered trademark. 3) Wetting agent manufactured by Daniel Product: interfacial tension modifier without silicone.

La peinture ou dispersion catalytique est appliquée sur un substrat polymérique, sans aucun prétraitement préalable de ce dernier, par trempage, pulvérisation, application au rouleau ou tampographie et est ensuite séchée à l'air pendant quelques secondes. Le film ainsi obtenu est irradié à l'aide de lampes UV communément utilisées et/ou de laser et ayant un spectre compris entre 250 et 450 nm, le temps nécessaire pour que le film reçoive une énergie minimale de 25 mJ/cm2. Si une métallisation sélective est désirée, cette irradiation se fera au travers d'un masque. Il en résulte le dépôt d'une couche de palladium catalytique sélective ou non. Dans le cas d'une métallisation sélective, les parties non irradiées sont solubilisées dans de l'eau. Une surcharge métallique par galvanoplastie est alors rendue possible, le substrat étant rendu conducteur.The catalytic paint or dispersion is applied to a polymeric substrate, without any pretreatment of the latter, by soaking, spraying, roller coating or pad printing and is then air-dried for a few seconds. The film thus obtained is irradiated with UV lamps commonly used and / or laser and having a spectrum between 250 and 450 nm, the time required for the film to receive a minimum energy of 25 mJ / cm 2 . If a selective metallization is desired, this irradiation will be done through a mask. This results in the deposition of a selective catalytic palladium layer or not. In the case of selective metallization, the non-irradiated parts are solubilized in water. A metal overload by electroplating is then made possible, the substrate being made conductive.

Exemple 2Example 2

Peinture catalytique au cuivre pour la métallisation sélective ou non d'un substrat polymérique. Composition de la dispersion Concentration en % en poids Dioxyde de titane en poudre finement divisée 5 à 25 Dioxanne 10 à 30 Acétate de 2-méthoxy-1-méthyléthyle 25 à 40 Mélange d'isomères d'éther méthylique de dipropylène glycol 1 à 15 Disperse-AYD® W331) 0,2 à 2 Joncry® 537 2) 5 à 25 Mélange d'isomères d'éther méthylique de tripropylène glycol 1 à 5 Dapro® U993) 0,25 à 1 Chlorure de palladium (II) (sel métallique) 0,05 à 1 Acide citrique (complexant) 0,1 à 1 Ammoniaque (base) 0,1 à 1 Eau désionisée 1 à 15 1) Agent dispersant fabriqué par la société Elementis : mélange d'agents tensioactifs non ionique et anionique dans de l'eau. 2) Emulsion polymérique acrylique filmogène, fabriquée par la société Johnson Polymer, marque déposée. 3) Agent mouillant fabriqué par la société Daniel Product : modificateur de tension interfaciale sans silicone. Copper catalytic paint for the selective metallization or not of a polymeric substrate. Composition of the dispersion Concentration in% by weight Finely divided titanium dioxide powder 5 to 25 dioxane 10 to 30 2-methoxy-1-methylethyl acetate 25 to 40 Mixture of dipropylene glycol methyl ether isomers 1 to 15 Disperse-AYD® W33 1) 0.2 to 2 Joncry® 537 2) 5 to 25 Mixture of tripropylene glycol methyl ether isomers 1 to 5 Dapro® U99 3) 0.25 to 1 Palladium (II) chloride (metal salt) 0.05 to 1 Citric acid (complexing) 0.1 to 1 Ammonia (base) 0.1 to 1 Deionized water 1 to 15 1) Dispersing agent manufactured by Elementis: a mixture of nonionic and anionic surfactants in water. 2) polymeric acrylic film-forming emulsion, manufactured by the company Johnson Polymer, registered trademark. 3) Wetting agent manufactured by Daniel Product: interfacial tension modifier without silicone.

On procède comme dans l'Exemple 1. Il en résulte le dépôt d'une couche de palladium catalytique sélective ou non. Dans le cas d'une métallisation sélective, les parties non irradiées sont solubilisées dans de l'eau. Une surcharge métallique par galvanoplastie est alors rendue possible.The procedure is as in Example 1. This results in the deposition of a selective catalytic palladium layer or not. In the case of selective metallization, the non-irradiated parts are solubilized in water. A metal overload by electroplating is then made possible.

En fait, le sel métallique pourrait être remplacé dans les concentrations indiquées par tous les sels cités spécifiquement, à savoir le sulfate de cuivre (II) et les chlorures de palladium et nickel (II).In fact, the metal salt could be replaced in the concentrations indicated by all the specifically mentioned salts, namely copper (II) sulphate and palladium and nickel (II) chlorides.

Les substrats testés dans le cadre des exemples précités sont des matières plastiques courantes telles que l'ABS, l'ABS-PC (polycarbonate), certains polyamides, les matières époxy, les polycarbonates et analogue.The substrates tested in the context of the abovementioned examples are common plastics such as ABS, ABS-PC (polycarbonate), certain polyamides, epoxy materials, polycarbonates and the like.

Outre les avantages clairement définis de la dispersion photosensible de l'invention comparativement aux résines polymériques ou autres formulations connues on notera que la dispersion est une formulation extrêmement proche d'une peinture la rendant facilement applicable en toutes circonstances. De plus, outre le fait qu'il n'est plus nécessaire de recourir à un prétraitement chimique et/ou mécanique du substrat isolant de manière à obtenir une bonne adhérence du dépôt métallique final de par l'oxydation sélective contrôlée de la surface du substrat par le pigment, la dispersion ou peinture catalytique photosensible de l'invention ne présente aucune corrosivité à l'inverse des formulations de la technique antérieure qui sont toutes très corrosives.In addition to the clearly defined advantages of the photosensitive dispersion of the invention compared with polymeric resins or other known formulations it will be appreciated that the dispersion is a formulation extremely close to a paint making it easily applicable in all circumstances. In addition, besides the fact that it is no longer necessary to resort to a chemical and / or mechanical pretreatment of the insulating substrate so as to obtain good adhesion of the final metal deposit by the controlled selective oxidation of the substrate surface. by the pigment, the dispersion or catalytic photosensitive paint of the invention has no corrosivity in contrast to the formulations of the prior art which are all very corrosive.

Il doit être entendu que la présente invention n'est en aucune façon limitée aux formes de réalisation décrites ci-dessus et que bien des modifications peuvent être apportées sans sortir du cadre du présent brevet.It should be understood that the present invention is in no way limited to the embodiments described above and that many modifications can be made without departing from the scope of this patent.

Claims (24)

  1. Photosensitive dispersion with adjustable viscosity for the deposition of metal on an insulating substrate, characterised in that it comprises, in combination, a pigment conferring properties of oxidation-reduction under light irradiation, a metallic salt, a sequestering agent for the metallic salt, a liquid film-forming polymeric formulation, a basic compound, an organic solvent and water.
  2. Dispersion according to Claim 1, characterised in that the said pigment is titanium dioxide.
  3. Dispersion according to Claim 2, characterised in that the titanium oxide pigment is in the form of a powder with a particle size of 10 nanometres to 10 micrometres, advantageously from 15 nanometres to 1 micrometre.
  4. Dispersion according to any one of Claims 1 to 3, characterised in that the metallic salt is a transition metal salt.
  5. Dispersion according to Claim 4, characterised in that the transition metal is chosen from the group comprising copper, gold, platinum, palladium, nickel, cobalt, silver, iron, zinc, cadmium, ruthenium and rhodium.
  6. Dispersion according to Claim 5, characterised in that the transition metal salt is chosen from amongst copper (II) chloride, copper (II) sulphate, palladium (II) chloride, nickel (II) chloride and mixtures of at least two of these.
  7. Dispersion according to any one of Claims 1 to 6, characterised in that the sequestering agent for the metallic salt is of the sulphate, chloride or carboxylic acid type.
  8. Dispersion according to Claim 7, characterised in that the sequestering agent of the carboxylic acid type is tartaric acid, citric acid, a derivative of these or a mixture thereof.
  9. Dispersion according to any one of Claims 1 to 8, characterised in that the liquid film-forming polymeric formulation is a solution or emulsion.
  10. Dispersion according to Claim 9, characterised in that it comprises, as a film-forming polymeric formulation, a solution of the alkyl, acrylic, polyester or epoxy type, an acrylic emulsion or a mixture of these.
  11. Dispersion according to any one of Claims 1 to 10, characterised in that the basic compound is a base, a basic salt or a mixture of these.
  12. Dispersion according to Claim 11, characterised in that the basic compound is a base chosen from amongst potassium hydroxide, sodium hydroxide and ammonia.
  13. Dispersion according to any one of Claims 1 to 12, characterised in that the organic solvent is chosen from a group comprising ethers, esters, ketones, alcohols and mixtures thereof.
  14. Dispersion according to Claim 13, characterised in that the organic solvent is chosen from amongst dioxane, cyclohexanone, 2-methoxy-1-methylethyl acetate, a mixture of dipropylene glycol methyl ether isomers, a mixture of tripropylene glycol methyl ether isomers and mixtures of at least two of these.
  15. Dispersion according to any one of Claims 1 to 14, characterised in that it comprises deionised water.
  16. Dispersion according to any one of Claims 1 to 15, characterised in that it comprises in addition at least one wetting agent, a dispersing agent or a mixture of these.
  17. Dispersion according to any one of Claims 2 to 16, characterised in that the concentration of titanium dioxide, as a percentage by weight, is 1% to 50% and preferably 5% to 25%.
  18. Dispersion according to any one of Claims 1 to 17, characterised in that the concentration of metallic salt, as a percentage by weight, is 0.01 % to 5% and preferably 0.05% to 1 %.
  19. Dispersion according to any one of Claims 1 to 18, characterised in that the concentration of sequestering agent, as a percentage by weight, is 0.01 % to 10% and preferably 0.1 % to 1 %.
  20. Dispersion according to any one of Claims 1 to 19, characterised in that the concentration of film-forming polymeric formulation, as a percentage by weight, is 1% to 50% and preferably 5% to 25%.
  21. Dispersion according to any one of Claims 12 to 20, characterised in that the concentration of base, as a percentage by weight, is 0.01 % to 5% and preferably 0.1 % to 1 %.
  22. Dispersion according to any one of Claims 1 to 21, characterised in that the concentration of organic solvent, as a percentage by weight, is 0.1 % to 55% and preferably 1 % to 40%.
  23. Dispersion according to any one of Claims 1 to 22, characterised in that the concentration of water, as a percentage by weight, is 1% to 15%.
  24. Method of depositing metal on the surface of an insulating substrate, using the photosensitive dispersion according to any one of Claims 1 to 23, characterised in that it comprises the application of the said dispersion in the form of a film on the substrate, selectively or not, the drying of the film applied to the said substrate and irradiation by means of ultraviolet radiation and/or laser with a range of wavelengths between 190 and 450 nm and an energy between 25 mJ/cm2 and 100 mJ/cm2 until a layer of metal, selective or not, is obtained on the substrate.
EP03782026A 2003-01-03 2003-12-24 Photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate and use of same Expired - Lifetime EP1587967B1 (en)

Priority Applications (1)

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SI200330267T SI1587967T1 (en) 2003-01-03 2003-12-24 Photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate and use of same

Applications Claiming Priority (3)

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BE2003/0007A BE1015271A3 (en) 2003-01-03 2003-01-03 Sensitive release adjustable viscosity for deposit metal on a substrate insulation and use.
BE200300007 2003-01-03
PCT/BE2003/000229 WO2004061157A1 (en) 2003-01-03 2003-12-24 Photosensitive dispersion with adjustable viscosity for metal deposition on an insulating substrate and use of same

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Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
JP2009056348A (en) * 2007-08-30 2009-03-19 Sumitomo Chemical Co Ltd Photocatalyst dispersion
RU2462537C2 (en) * 2010-11-11 2012-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет Solution for laser-induced metallisation of dielectric materials, and method of laser-induced metallisation of dielectric materials using it
JP2013000673A (en) * 2011-06-17 2013-01-07 National Institute Of Advanced Industrial Science & Technology Technology for enhancing performance of photocatalyst
RU2491306C2 (en) * 2011-07-20 2013-08-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В.Ломоносова) Rubber mixtures based on diene and ethylenepropylene caoutchoucs, filled with silica white
US10049881B2 (en) * 2011-08-10 2018-08-14 Applied Materials, Inc. Method and apparatus for selective nitridation process
WO2014017575A1 (en) * 2012-07-26 2014-01-30 株式会社サクラクレパス Photocatalyst coating liquid, method for producing same, and photocatalyst
DE102013114572A1 (en) 2013-12-19 2015-06-25 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Process for producing structured metallic coatings
CN104329597B (en) * 2014-09-10 2016-11-23 广东中塑新材料有限公司 A kind of without substrate LED and preparation method thereof
CN111575097B (en) * 2020-06-15 2021-04-16 清华大学 Solution with optically variable viscosity and method for regulating fluid viscosity

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719490A (en) * 1967-07-13 1973-03-06 Eastman Kodak Co Photosensitive element containing a photoreducible palladium compound and the use thereof in physical development
US3950290A (en) * 1973-05-01 1976-04-13 A. E. Staley Manufacturing Company Aqueous coating and printing compositions
JPS60155678A (en) * 1984-01-24 1985-08-15 Toshiba Corp Method for reducing metallic ion
JPS60195077A (en) * 1984-03-16 1985-10-03 奥野製薬工業株式会社 Catalyst composition for ceramic electroless plating
JPS62109393A (en) * 1985-11-07 1987-05-20 カルソニックカンセイ株式会社 Manufacture of electric circuit substrate
JPH02205388A (en) * 1989-02-03 1990-08-15 Hitachi Chem Co Ltd Manufacture of printed circuit by electroless plating using semiconductor optical catalyst
US5075039A (en) * 1990-05-31 1991-12-24 Shipley Company Inc. Platable liquid film forming coating composition containing conductive metal sulfide coated inert inorganic particles
US5405879A (en) * 1991-04-05 1995-04-11 Nippon Carbide Kogyo Kabushiki Kaisha Aqueous dispersion of acrylic polymer
US5264466A (en) * 1992-05-28 1993-11-23 Showa Highpolymer Co., Ltd. Stainproofing paint composition and method for producing same
BE1007879A3 (en) * 1994-01-05 1995-11-07 Blue Chips Holding Polymer resin viscosity adjustable for filing on palladium catalyst substrate, method of preparation and use.
CA2188148A1 (en) * 1994-04-19 1995-10-26 John W. Vanderhoff Printing ink compositions, methods for making same and uses thereof
US6183944B1 (en) * 1995-11-30 2001-02-06 Eastman Kodak Company Aggregated dyes for radiation-sensitive elements
JP3384544B2 (en) * 1997-08-08 2003-03-10 大日本印刷株式会社 Pattern forming body and pattern forming method
US6291025B1 (en) * 1999-06-04 2001-09-18 Argonide Corporation Electroless coatings formed from organic liquids
DE19957130A1 (en) * 1999-11-26 2001-05-31 Infineon Technologies Ag Metallizing dielectric materials comprises applying a photosensitive dielectric to a substrate, irradiating the dielectric through a mask, growing a metal, subjecting to high temperatures and chemically metallizing
JP2001152362A (en) * 1999-11-30 2001-06-05 Nisshin Steel Co Ltd Photocatalyst-coated metallic sheet
JP3449617B2 (en) * 2000-09-26 2003-09-22 日本カーリット株式会社 Metal oxide thin film and method for forming the same
GB0025989D0 (en) * 2000-10-24 2000-12-13 Shipley Co Llc Plating catalysts
FR2824846B1 (en) * 2001-05-16 2004-04-02 Saint Gobain SUBSTRATE WITH PHOTOCATALYTIC COATING
JP2004136644A (en) * 2002-08-20 2004-05-13 Konica Minolta Holdings Inc Ink jet recording paper

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US20060122297A1 (en) 2006-06-08
DK1587967T3 (en) 2006-08-28
AU2003289778B2 (en) 2009-06-04
BE1015271A3 (en) 2004-12-07
RU2301846C2 (en) 2007-06-27
KR100777033B1 (en) 2007-11-16
IL169463A (en) 2009-12-24
CA2512202A1 (en) 2004-07-22
JP2006515388A (en) 2006-05-25
PT1587967E (en) 2006-08-31
WO2004061157A1 (en) 2004-07-22
US7731786B2 (en) 2010-06-08
CA2512202C (en) 2010-11-09
AU2003289778A1 (en) 2004-07-29
BR0317897A (en) 2005-12-06
CN100587110C (en) 2010-02-03
DE60305213D1 (en) 2006-06-14
JP4621505B2 (en) 2011-01-26
ATE325907T1 (en) 2006-06-15
ZA200505512B (en) 2007-02-28
KR20050089087A (en) 2005-09-07
DE60305213T2 (en) 2007-03-01
ES2261991T3 (en) 2006-11-16
CN1735712A (en) 2006-02-15
US20090017221A1 (en) 2009-01-15
EP1587967A1 (en) 2005-10-26
RU2005124683A (en) 2006-02-10
MXPA05007256A (en) 2005-09-08
BR0317897B1 (en) 2012-07-10

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