EP1587967B1 - Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung - Google Patents

Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung 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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dispersion according
dispersion
concentration
percentage
weight
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French (fr)
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EP1587967A1 (de
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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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
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  • 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)
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Claims (24)

  1. Photosensible Dispersion mit einstellbarer Viskosität für die Abscheidung vom Metall auf einem nicht leitenden Substrat, dadurch gekennzeichnet, dass sie, in Kombination, ein Pigment, das unter Bestrahlung mit Licht Redoxeigenschaften verleiht, ein metallisches Salz, einen Komplexbildner für das metallische Salz, eine flüssige, filmbildende polymerische Formulierung, eine basische Verbindung, ein organisches Lösemittel und Wasser umfasst.
  2. Dispersion gemäß Anspruch 1, dadurch gekennzeichnet, dass das Pigment Titandioxid ist.
  3. Dispersion gemäß Anspruch 2, dadurch gekennzeichnet, dass das Titanoxidpigment in Pulverform mit einer Partikelgröße zwischen 10 Nanometer und 10 Mikrometer, vorteilhafterweise zwischen 15 Nanometer und 1 Mikrometer vorliegt.
  4. Dispersion gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das metallische Salz ein Übergangsmetallsalz ist.
  5. Dispersion gemäß Anspruch 4, dadurch gekennzeichnet, dass das Übergangsmetall ausgewählt wird aus der Gruppe, bestehend aus Kupfer, Gold, Platin, Palladium, Nickel, Kobalt, Silber, Eisen, Zink, Kadmium, Ruthenium und Rhodium.
  6. Dispersion gemäß Anspruch 5, dadurch gekennzeichnet, dass das Übergangsmetallsalz ausgewählt wird aus Kupferchlorid (II), Kupfersulfat (II), Palladiumchlorid (II), Nickelchlorid (II) und Mischungen von mindestens zwei daraus.
  7. Dispersion gemäß einer der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Komplexbildner für das metallische Salz Karbonsäure, ein Chlorid oder ein Sulfat ist.
  8. Dispersion gemäß Anspruch 7, dadurch gekennzeichnet, dass der Komplexbildner Karbonsäure, Weinsäure, Zitronensäure, ein Derivat dieser Säuren oder eine Mischung daraus ist.
  9. Dispersion gemäß einer der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die flüssige, filmbildende, polymerische Flüssigkeit eine Lösung oder eine Emulsion ist.
  10. Dispersion gemäß Anspruch 9, dadurch gekennzeichnet, dass sie als polymerische filmbildende Formulierung eine Alkyl-, Acryl-, Polyester- oder Epoxidlösung, eine Acrylemulsion oder eine Mischung daraus, umfasst.
  11. Dispersion gemäß einer der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die basische Verbindung eine Base, ein basisches Salz oder eine Mischung daraus ist.
  12. Dispersion gemäß Anspruch 11, dadurch gekennzeichnet, dass die basische Verbindung eine Base, ausgewählt aus Kaliumhydroxid, Natriumhydroxid und Ammoniak ist.
  13. Dispersion gemäß einer der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass das organische Lösemittel ausgewählt wird aus der Gruppe, die Ether, Ester, Ketone, Alkohole und Mischungen daraus umfasst.
  14. Dispersion gemäß Anspruch 13, dadurch gekennzeichnet, dass das organische Lösemittel aus Dioxan, Cyclohexanon, 2-Methoxy-1-methylethylacetat, einer Mischung aus Methyletherisomeren von Dipropylenglycol, einer Mischung aus Methyletherisomeren von Tripropylenglycol und den Mischungen von mindestens zwei daraus, ausgewählt wird.
  15. Dispersion gemäß einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass sie deionisiertes Wasser umfasst.
  16. Dispersion gemäß einer der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass sie außerdem ein Netzmittel, ein Dispersionsmittel oder eine Mischung daraus umfasst.
  17. Dispersion gemäß einer der Ansprüche 2 bis 16, dadurch gekennzeichnet, dass die Titandioxidkonzentration, in Gewichtsprozent, zwischen 1 und 50 Gew.-% und vorzugsweise zwischen 5 und 25 Gew.-% liegt.
  18. Dispersion gemäß einer der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass die Konzentration an metallischem Salz, in Gewichtsprozent, zwischen 0,01 und 5 Gew.-% und vorzugsweise zwischen 0,05 und 1 Gew.-% liegt.
  19. Dispersion gemäß einer der Ansprüche 1 bis 18, dadurch gekennzeichnet, dass die Konzentration an Komplexbildner, in Gewichtsprozent, zwischen 0,01 und 10 Gew.-% und vorzugsweise zwischen 0,1 und 1 Gew.-% liegt.
  20. Dispersion gemäß einer der Ansprüche 1 bis 19, dadurch gekennzeichnet, dass die Konzentration an polymerischer filmbildender Formulierung, in Gewichtsprozent, zwischen 1 und 50 Gew.-% und vorzugsweise zwischen 5 und 25 Gew.-% liegt.
  21. Dispersion gemäß einer der Ansprüche 12 bis 20, dadurch gekennzeichnet, dass die Basekonzentration, in Gewichtsprozent, zwischen 0,01 und 5 Gew.-% und vorzugsweise zwischen 0,1 und 1 Gew.-% liegt.
  22. Dispersion gemäß einer der Ansprüche 1 bis 21, dadurch gekennzeichnet, dass die Konzentration an organischem Lösemittel, in Gewichtsprozent, zwischen 0,1 und 55 Gew.-% und vorzugsweise zwischen 1 und 40 Gew.-% liegt.
  23. Dispersion gemäß einer der Ansprüche 1 bis 22, dadurch gekennzeichnet, dass die Konzentration an Wasser, in Gewichtsprozent, zwischen 1 und 15 Gew.-% liegt.
  24. Verfahren zur Abscheidung vom Metall auf der Oberfläche eines nicht leitenden Substrats mit Hilfe der photosensiblen Dispersion gemäß einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, dass sie den Auftrag der Dispersion in Form eines Films auf dem Substrat auf selektive oder nicht selektive Weise, die Trocknung des auf dem Substrat aufgetragenen Films und die Bestrahlung mit Hilfe ultravioletter Strahlung und/oder Laser aus einem Wellenlängenbereich zwischen 190 und 450 nm und einem Energiebereich zwischen 25 mJ/cm2 bis 100 mJ/cm2 bis zum Erhalt einer selektiven oder nicht selektiven Metallschicht auf dem Substrat umfasst.
EP03782026A 2003-01-03 2003-12-24 Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung Expired - Lifetime EP1587967B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200330267T SI1587967T1 (sl) 2003-01-03 2003-12-24 Fotosenzibilna disperzija z nastavljivo viskoznostjo za nanasanje kovine na izolirno podlago in njena uporaba

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Application Number Priority Date Filing Date Title
BE2003/0007A BE1015271A3 (fr) 2003-01-03 2003-01-03 Dispersion photosensible a viscosite ajustable pour le depot de metal sur un substrat isolant et son utilisation.
BE200300007 2003-01-03
PCT/BE2003/000229 WO2004061157A1 (fr) 2003-01-03 2003-12-24 Dispersion photosensible a viscosite ajustable pour le depot de metal sur un substrat isolant et son utilisation

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EP1587967B1 true EP1587967B1 (de) 2006-05-10

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US (2) US20060122297A1 (de)
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JP (1) JP4621505B2 (de)
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CN (1) CN100587110C (de)
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BE (1) BE1015271A3 (de)
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CA (1) CA2512202C (de)
DE (1) DE60305213T2 (de)
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ES (1) ES2261991T3 (de)
IL (1) IL169463A (de)
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PT (1) PT1587967E (de)
RU (1) RU2301846C2 (de)
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ZA (1) ZA200505512B (de)

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RU2491306C2 (ru) * 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) Резиновые смеси на основе диеновых и этиленпропиленовых каучуков, наполненные белой сажей
US10049881B2 (en) * 2011-08-10 2018-08-14 Applied Materials, Inc. Method and apparatus for selective nitridation process
JPWO2014017575A1 (ja) * 2012-07-26 2016-07-11 株式会社サクラクレパス 光触媒塗布液およびその製造方法並びに光触媒体
DE102013114572A1 (de) 2013-12-19 2015-06-25 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Verfahren zur Herstellung strukturierter metallischer Beschichtungen
CN104329597B (zh) * 2014-09-10 2016-11-23 广东中塑新材料有限公司 一种无基板led灯及其制备方法
CN111575097B (zh) * 2020-06-15 2021-04-16 清华大学 具有光致变粘度的溶液及调控流体粘度的方法

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

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