US3682671A - Novel precious metal sensitizing solutions - Google Patents
Novel precious metal sensitizing solutions Download PDFInfo
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- US3682671A US3682671A US3682671DA US3682671A US 3682671 A US3682671 A US 3682671A US 3682671D A US3682671D A US 3682671DA US 3682671 A US3682671 A US 3682671A
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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
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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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
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
-
- 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
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
Definitions
- Optically clear sensitizing solutions for rendering surfaces receptive to the deposition of an adherent electroless metal comprise water and a metal complex consisting of (a) a precious metal selected from a group consisting of the precious metals of the fifth and sixth periods of Groups VIII and I-B of the Periodic Table of Elements, (b) a Group *IV metal of the Periodic Table of Elements which is capable of two valence states and (c) an anion capable of forming a stable moiety with both valence states of the Group IV metal, in which the molar ratio of (a) to (b) to (c) is from about 1:1:3 to 1:6:24.
- the solutions can be prepared directly from the components or, preferably, by diluting a concentrate.
- the solutions can be stabilized against precious metal separation by adding an organic mono-o1, diol or polyol, a fiuorinated hydrocarbon wetting agent or hydrogen fluoride.
- Processes for rendering surfaces receptive to the deposition of an electroless metal are also provided in which there are employed the new sensitizing solutions.
- the subject matter of the present invention relates to new and useful precious metal sensitizing solutions. More particularly, the invention relates to solutions comprising a precious metal complex, and to concentrates thereof. The solutions are used to render surfaces of a substrate catalytic to the reception of an electroless metal.
- the plural bath process while readily effecting sensitization, deposits on metals a flash coating of the precious metal from the sensitizing bath.
- the precious metal so flash coated from the sensitizing bath disrupts the balance of the bath.
- the addition of the precious metal bearing solution to the bath is required. This, of course, increases the cost of the plural bath process.
- flash coating of precious metal normally leads to a low grade of adhesion, thereby materially affecting the bond and peel strength of an electroless metal deposit.
- the unitary bath process on the other hand, While overcoming the problem of flash coating, has a diminished reactivity and requires longer periods of time for sensitization. Moreover, because colloids are involved, concentrates of such baths can not be prepared and shipped or stored because of destruction of the colloidal dispersion by flocculation. Concentrated unitary bath sensitizers are desirable because shipping and storage costs will be minimized; and process solutions are more simply put together (by dilution, for example).
- Another object of the present invention is to provide new and useful stabilized compositions which are true solutions and methods for sensitizing substrates using them which substantially obviate the problem of non-adherent precious metal flash coatings.
- Yet another object of the invention is to provide dilutable, concentrated compositions and methods for sensitizing substrates with a precious metal which involves using very dilute treating solutions and thereby materially diminishing production costs.
- the present invention relates to sensitizing solutions for rendering surfaces receptive to the deposition of an adherent electroless metal which comprise water and a metal complex consisting of three components:
- a precious metal selected from the group consisting of the precious metals of the fifth and sixth periods of Groups VIII and I-B of the Periodic Table of Elements;
- compositions, dilutable to optically-clear sensitizing solutions for rendering surfaces receptive to the deposition of an adherent electroless metal which comprise water and a metal complex consisting of three components: (a) a precious metal selected from the group consisting of the precious metals of the fifth and sixth periods of Groups VIII and I-B of the Periodic Table of Elements; (b) a Group IV metal of the Periodic Table of Elements, which is capable of two valence states; and (c) an anion capable of forming a stable moiety with both valence states of the Group IV metal, in which the molar ratio of precious metal to Group IV metal to anion is from about 1:1:3 to 1:624, and wherein the concentration of component (a) is at least about 1.5 grams/liter.
- a preferred feature of the invention is a stabilized solution as above defined which includes a stabilizing amount of an organic mono-o1, diol or polyol, a fiuorinated hydrocarbon wetting agent or hydrogen fluoride.
- This embodiment is: a stabilized solution for rendering a surface receptive to the deposition of an adherent electroless metal which comprises water; a metal complex consisting of three components (a), (b) and (c) as defined above, the molar ratios of components (a) to (b) to being from about 1:1:3 to 1:6:24; and, as a stabilizing ingredient, a compound selected from the group consisting of organic mono-01s, diols and polyols, i.e., monohydroxy, dihydroxy and polyhydroxy organic compounds, a fiuorinated hydrocarbon wetting agent or hydrogen fluoride, the amount of said compound in said solution being at least sufficient to prevent separation therefrom of component (a) as a metallic film or precipitate.
- optically-clear sensitizing solutions which have been prepared by diluting the concentrates with water, an acid or a mixture of water and an acid, until the concentration of component (a) has been reduced to a concentration of from about 0.0003 grams/ liter to about 1.5 grams/liter.
- Another feature of the invention is a process to prepare the concentrate comprising heating an aqueous mixture of the components (a), (b) and (c) at a temperature of from about 80 C. to about the boiling point until formation of the complex is complete.
- Still another feature is a process to prepare the concentrate which comprises mixing an aqueous solution of components (a) and (c) with an aqueous solution of components (b) and (c) and heating the mixture at from 80 C. to its boiling point.
- the present invention further relates to an improved process for rendering surfaces receptive to the deposition of an adherent electroless metal, as well as a process for electrolessly depositing a metal on a substrate which has been sensitized with the sensitizing solutions of the present invention.
- An additional embodiment of the invention relates to particular acidic precious metal solutions for rendering surfaces receptive to the deposition of electroless copper.
- the invention consists of the novel methods, processes, steps and improvements shown and described.
- the present invention provides a significant improvement over the known sensitization techniques and compositions in that a procedure and composition is provided which will cause conductive and non-conductive materials to be so sensitized simultaneously that eflicient and uniform deposition of an adhering electroless metal thereon may be readily effective; thus permitting, by way of illustration, copper plating of the non-metallic surfaces of the side walls of the apertures defined in a plastic base material, as well as the concomitant adherent electroless deposition of copper on pre-formed copper surfaces on the plastic base.
- Illustrative of the conductive and nonconductive, metallic and non-metallic surfaces which can be plated uniformly with adherent electroless metal by use of the sensitizing solutions and techniques of the present invention are plastic surfaces and surfaces of metallic copper, iron-nickel, cobalt, silver, gold and alloys thereof, such as stainless steel, brass, sterling silver and the like.
- the present invention can be employed to render a surface catalytic to the reception of such metals as copper, nickel, palladium, cobalt, silver, gold, and the like.
- a further advantage of the present invention is that sensitization as taught herein leads to practically complete avoidance of the deposition of a flash coating of precious metal from the sensitizing bath.
- a flash coating of precious metal normally leads to a low grade of adhesion. Also, avoidance of such deposition economically conserves the precious metal.
- the sensitizing solution can be directly incorporated in a plastic base at the time of its manufacture. This can be achieved by utilizing an organic sensitizing solution employing a solvent such as cyclohexanone, or a highly viscous paste like composition. Alternatively, the solution can be reduced to a solid form by employing a counter ion and directly incorporating such solid in a plastic base at the time of manufacture. Therefore, the advent of the prsent invention provides for the preparation of presensitized plastic solutions.
- the most notable advantage occasioned by the advent of the present invention resides in the fact that such solutions possess a sensitizing activity at dilute levels.
- a complex is formed between the metals and the anion.
- the preferred palladium-tin-chloride complex of this invention for example, in addition to being acid soluble, is soluble in organic solvents, e.g., dimethylformamide, cyclohexanone, hexane, dimethyl sulfoxide, and the like. It is optically clear in dilute solution. It is filterable through ultra-membranes through which colloidal sensitizers will not pass.
- concentrates of the complex according to this invention may be diluted to levels of concentration which cannot easily and reproducibly be directly formulated in active sensitizing solutions.
- the invention makes available stable sensitizing solutions comprising significantly lower concentrations of precious metal than can be produced by other known methods.
- the treating or sensitization procedure which is an embodiment of this invention is an intermediate step between pretreatment or cleaning of the surfaces upon which the metal is to be electrolessly deposited and the actual deposition of the metal.
- the treatment to be afforded the surface to be plated depends upon the cleanliness of the material to be treated and associated factors.
- the first step in the procedure for effecting deposition of adherent electroless metal is to clean thoroughly the article or panel upon which plating is to occur. This is desirably accomplished by scrubbing the panel with pumice or the like to remove heavy soils; rinsing with water; and subsequent removal of soiling due to organic substances from the panel and apertures defined therein with a suitable alkali cleaning composition.
- a typical alkaline cleaner composition is as follows:
- Oxides are removed from copper panel surfaces and apertures by application of a light etching solution such as a 25 percent solution of ammonium persulfate in water as is described in Bulletin No. 86 of the Becco Chemical Division of the Food Machinery and Chemical Corporation, Buifalo, NY.
- the surface oxides also may be removed by application of the cupric chloride etchant solution described by Black in US. Pat. No. 2,908,557. This treatment should not exceed 2 to 3 minutes.
- the treatment period and temperature are significant, particularly where the panel surfaces are formed of a conductive metal, in that elevated temperatures and extended periods of time beyond those described may result in removal not only of the oxide materials but of the conductive metal, such as copper foil, forming the surfaces of the panel.
- the panel is rinsed thoroughly after this step with water to remove all semblance of etching compounds. Care should be taken to avoid the formation of further oxide film during rinsing or as a result of air oxidation.
- the panel may be inserted in a hydrochloric acid solution comprising 42 fluid ounces of hydrochloric acid per gallon of water for a period of from 2 to 5 minutes, and from this bath the panel is placed in the sensitization or treating solution of the present invention.
- a sanding operation with a fine abrasive can also be used to remove oxides.
- the sensitizing solution comprises an aqueous solution of a metal complex as defined above consisting of (a) a precious metal, (b) a Group IV metal and (c) an anion. It is optically-clear, i.e., non-colloidal.
- precious metals that may be mentioned are palladium, platinum, gold, rhodium, osmium, iridium and mixtures of these metals.
- the inorganic and organic acid salts of these metals, and of the Group IV metals such as the chlorides, bromides, fluorides, fluoroborates, iodides, nitrates, sulfates and acetates of stannous tin, titanium and germanium among others may be used.
- the salts are preferably soluble in water, or in organic or inorganic acid aqueous solutions.
- the chloride is preferred, both for the precious metal, and the Group IV metal compound.
- the preferred precious metals and Group IV metal are palladium or platinum, particularly palladium and stannous tin.
- the concentration of the precious metal ion in the concentrates will be at least about 1.5 grams/liter.
- the upper limit will be about 100 grams/liter.
- the precious metal concentration should be from at least about 0.0003 to about 1.5 grams/ liter of solution. While the higher end of this range causes sensitization to be completed in very abbreviated periods of time, e.g., ten seconds, the lower end of this range is normally more economic.
- the bath can be prepared directly or by diluting a concentrate.
- the concentrates as defined above are diluted with Water or an aqueous solution of suitable acid.
- the concentrates are prepared by heating the salts of the precious metals and a Group IV metal salt in an aqueous solution of suitable acid as will be described hereinafter.
- suitable acid include hydrochloric acid, hydrofluoric acid, fluoboric acid, hydroiodic acid, sulfuric acid and acetic acid.
- the anion of the inorganic acid corresponds to the anion of the salt of the precious metals, or to the anion of the Group IV metal salt.
- the anion of the acid should preferably correspond to the common anion of the salts.
- the anion of the acid preferably corresponds to the anion of the precious metal salt.
- acids having anions which differ from the anions of the precious metal salts or of the Group IV metal salt may also be used.
- Preferred anions are Cland SnCl.
- the concentration of the acid in the sensitizing solution approaches the upper limit given hereinabove.
- the concentration of acid in the sensitizing solution should, of course, be high enough to solubilize the salts of the precious metals and the Group IV metal and also high enough to render the solution suitable for use as a sensitizer for the material being treated. Care should be used in selecting the acid concentration to insure that the specimen being treated is not adversely attacked or corroded by the treating solution.
- the Group IV metal ion concentration may vary widely but must be maintained in excess of a stoichiometric amount based on the amount of precious metal ions present in the sensitizing solution. Normally a large excess of, for example, stannous chloride, is maintained to allow for air oxidation of the stannous ion. Illustratively, concentrations of as high as 50 grams per liter of stannous chloride are not detrimental to the effectiveness of the sensitizing activity of the diluted solutions.
- the sensitizing solutions and concentrates thereof, of the present invention may contain additional agents to stabilize the solution, e.g., against the effects of atmospheric oxidation.
- agents will include the use of additional quantities of the Group IV metal, as for example, additional stannous chloride may be added to a palladium, stannous chloride sensitizing solution, as well as compounds, such as organic ols, diols and polyols, the fluorinated hydrocarbon wetting agents and hydrogen fluoride.
- additional agents may include the use of additional quantities of the Group IV metal, as for example, additional stannous chloride may be added to a palladium, stannous chloride sensitizing solution, as well as compounds, such as organic ols, diols and polyols, the fluorinated hydrocarbon wetting agents and hydrogen fluoride.
- One result of the addition of such compounds to the sensitizing solution is the prevention of oxidation of the Group IV metals and the subsequent reduction of the precious metals.
- stabilizing ingredients to the sensitizing solutions of this invention improves the stability of the solutions and avoids formation of precious metal residues on surfaces, e.g., metal surfaces, exposed to such solutions.
- the nature of the stabilizing ingredients is not particularly critical. It should be soluble at least in an amount great enough to provide the desired stabilization effect. Evidence of effective stabilization is easily observed in comparison with control baths, i.e., those without the stabilizing ingredient present. These latter baths over a period of one week or so will be seen to deposit a metallic film of precious metals or to deposit a precipitate of precious metal.
- the stabilizing ingredient need not be completely water soluble, although for ease of formulation a high degree of water solubility is desirable.
- the hydroxy compounds which can be used most efiiciently would be of relatively low molecular weight, polysubstituted with hydroxy groups or containing at least one hydroxy group and other functional groups such as sulfonic acid groups, phosphate groups, amino groups, halogens, carboxyl groups and the like, which tend to enhance solubility in polar media.
- the solubilizing group can be organic or inorganic, anionic, cationic, nonionic, amphoteric and water soluble.
- the wetting agents should be active in acidic solutions and have good thermal stability. Especially preferred are those wherein Z is anionic.
- a preferred species has the following spectrum of solubilities in acid media, in grams/ 1000 grams of solution: 12 /2% hydrochloric acid, 1; 37% hydrochloric acid, 0.1; 12 /z% nitric acid, 1; 70% nitric acid, 5; 12 /2% phosphoric acid, 1; 85% phosphoric acid, 1; 12 /z% sulfuric acid, and 97% sulfuric acid, 0.5.
- Another preferred species has the following solubility spectrum: 12 /2% hydrochloric acid, 10; 12 /2% nitric acid, 20; and 12 /2% sulfuric acid, 10.
- Particularly useful fluorinated hydrocarbon wetting agents of this type are sold under the trade name Fluorad by the Minnesota Mining and Manufacturing Company, St. Paul, Minn.
- the preferred species, described above, are designated Fluorad FC-95 and WG-98, respectively.
- Preferred hydroxyl-containing stabilizing ingredients are open chain aliphatic mono-01s, diols or polyols of from about 1 to about 12 carbon atoms, e.g., methanol, ethanol, i-propanol, ethylene glycol, propylene glycol, 1,4-butane diol, glycerol, glucose, sucrose, and the like; and closed chain aliphatic or aromatic monoor di-carbocyclic mono-01s, diols or polyols of from about 6 to about 12 carbon atoms, e.g., cyclohexanol, cyclohexanediol, inositol, phenol, fl-naphthol, resorcinol, catechol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, and the like.
- these stabilizing ingredients have a water solubility of at least greater than about 4% by weight, especially those in the aromatic family.
- Particularly preferred stabilizing ingredients of this type are isopropanol, ethylene glycol, glycerol, resorcinol, catechol, hydroquinone, pyrogallol and phloroglucinol. These can generally be employed at an appropriate concentration in the range of from about 2 to about 50% by weight in the final mixture.
- the aromatic compounds will be employed at 2 to 7 wt. percent and the aliphatic compounds will be used in concentrations of from about 4 to 50 wt. percent, although higher and lower amounts can be formulated, as mentioned above.
- An especially preferred stabilizer is resorcinol at 20 to 70 grams/liter.
- Illustrative fluorinated hydrocarbon Wetting agents have a formula selected from the group consisting of C 12,, CO-Z and wherein n is an integer of from 3 through 10, and Z is a hydrophilic group.
- surfactants are composed of molecules containing a perfluorinated tail portion and a hydrophilic head portion.
- the fluorocarbon portion of the molecules advantageously contains either 3 or 7 carbon atoms where the surfactant is a perfluorocarboxylic acid derivative, and 8 or 10 carbon atoms where the surfactant is a perfluorosulfonic acid derivative.
- hydrophilic portion of the fluorocarbon surfactants can be any typical hydrophilic group such as hydroxyl, alkali metal or alkaline earth metal substituted hydroxyl, an alkali metal group, an ammonium group,
- the hydrophilic tail portion of the radical can be a nitrogen-containing group having an amino or amido nitrogen or both.
- These can generally be employed at a concentration of from about 0.010 to 5.0 grams per liter in the final mixture, although higher and lower amounts can be formulated. Preferred results are obtained with from 0.025 to 1.0 g./liter and an especially good balance of stability and economy is obtained with 0.05 g./liter of the fluorinated surfactants.
- An illustrative surfactant for this embodiment of the invention has the formula: C F SO H. Useful too is hydrogen fluoride itself. This will be employed at 1 to 10 g./liter of solution and preferably at about 3 g./liter. Conveniently, this latter concentration is made by adding enough 60% aqueous HF to provide 50 ml./ liter.
- complexing reaction which occurs between the metals and the anion results in the formation of more than one and possibly several complexes.
- these can be depicted as including complex anions of the formula mixtures thereof, wherein Me is Ru, Rh, Pd, Os, Ir, Pt, Au or a mixture thereof.
- Preferred complexes are those wherein Me is Pd or Pt.
- the concentrations of the components of the complex are expressed in terms of molar ratio. Therefore, the molar ratio of precious metal to Group IV metal to anion of the complexes of the present invention is from about 1:1:3 to 1:6:24.
- the aqueous solutions of components be added to each other and mixed so that the components of the aqueous solutions do not react to form a collodial dispersion or colloidal agglomerates.
- the components of the solutions will react and the mixed, reacted solutions, will form a colloidal dispersion of palladium with a portion of the colloidal palladium precipitated and agglomerated.
- colloidal dispersion is not the clear sensitizing solution of the present invention nor does such colloidal dispersion result in the improved sensitizing solution of the present invention nor the improved electroless plating resulting from such clear sensitizing solution.
- One method found acceptable for producing a clear solution when the aqueous solutions of components are mixed, is to dissolve the palladium chloride in a so1ution of hydrochloric acid and water and to quickly dissolve the stannous chloride in the palladium chloride.
- the stannous chloride acts as a reducing agent and the high concentration of stannous tin forms a complex with the palladium chloride and prevents the reduction of palladium chloride to metallic palladium.
- the palladium chloride and stannous chloride may be separately dissolved in equal portions of water, hydrochloric acid solution and then mixed together. Such solution must be aged for at least one hour at 25 C. before use. While aging, the color of the solution mixture will change from green to dark brown, indicating that the proper stannous chloride, palladium chloride acid salts have formed and that the solution is ready for use.
- sensitizing solutions of the instant invention can be prepared as concentrates which may be stored, and shipped and diluted when the sensitizing solution is to be used for electroless plating.
- diluted concentrates form true, clear solutions.
- the concentrates of this invention can be prepared in oneor two-steps:
- an aqueous mixture which contains components (a), (b) and (c), as defined above, in which mixture component (a) is present in a concentration of at least about 2.5 grams/liter, the molar ratios of (a) to (b) to (c) each being, respectively, 1: at least 1: at least 3; is heated at a temperature of from about 80 C. to about the boiling point of the mixture until formation of the metal complex is substantially complete.
- an aqueous solution containing a salt of component (a) in a concentration of from about 2.5 grams per liter up to about the limit of solubility of the salt in water at the boiling point and component (c); and an aqueous solution of components (b) and (c), the ratios of (a):(b):(c) each being respectively, 1: at least about 1: at least about 3, are first prepared.
- the two solutions are mixed together and heated at a temperature of from about 80 C. to about the boiling point of the mixture until formation of the complex is substantially complete.
- palladium 4.8 to 100 grams/liter (calculated as metal) can be conveniently used. Depending on the temperature, it is preferred to heat the mixture for from about to 90 minutes, although this is not critical.
- a first solution comprising the following ingredients:
- Example 2 Stable, concentrated compositions, dilutable to opticallyclear sensitizing solutions are prepared, according to Example 1.
- the first solutions comprise, respectively:
- Example 3 A stable, concentrated composition, dilutable to an optically-clear sensitizing solution is prepared in one step.
- the following formulation is used:
- Palladium chloride (g.) 62.5 Hydrochloric arid (37%) (ml.) 700 Stannous chloride dihydrate (g.) 800 Water to make total (ml.) 1295 Stannous chloride is dissolved in the hydrochloric acid, then the water is added. The palladium chloride is added with agitation. The mixture is heated to C. for 20 minutes, then boiled for 1.5 hours and cooled.
- Example 4 A first solution is prepared comprising the following ingredients:
- Palladium chloride (g.) 10 Hydrochloric acid (37%, ml.) 200 Water to make total .(ml.) 500 The palladium salt dissolves slowly in the acid-water mixture.
- a second solution comprising the following ingredients:
- the mixture is allowed to col and there is obtained a concentrate according to this invention which contains palladium in a concentration of about 4.8 grams/liter.
- Example 5 The procedure of Example 1 is repeated, respectively substituting for the palladium chloride, stoichiometricallyequivalent amounts of the following: ruthenium chloride (RuCl rhodium chloride (RhCl osmium chloride (OsCl iridium chloride (IrCl and platinum chloride .(PtCl Concentrates according to this invention containing, respectively, about 30 grams/liter of ruthenium, rhodium, osmium, iridium and platinum are obtained.
- Example 6 A sensitizing solution according to this invention is prepared by taking 20 ml. of the concentrate from Example 1, diluting it with a mixture comprising 490 ml. of 37 percent hydrochloric acid and 490 ml. of water. The resulting solution will contain about 0.6 grams/liter of palladium in the form of the paladium-Stannous chloride complex of this invention and will have good catalytic activity.
- catalytically active sensitizing solu tions are prepared by taking 0.01 ml. and 50 ml. portions of the concentrate of Example 1 and diluting them, respectively, to 1 liter in 1:1 by volume of a mixture of 37% aqueous hydrochloric acid and water.
- the solutions contain, respectively, 0.0003 grams and 1.5 grams of paladium per liter.
- Example 7 The concentrates of Example 5 are diluted with enough 1:1 mixture by volume of 37% hydrochloric acid and water to provide sensitizing solutions according to this invention containing, respectively, 0.0006, 0.6 and 1.5 grams/liter of ruthenium, rhodium, osmium, iridium and platinum.
- the palladium chloride is an aliquot of a solution containing PdCl and 37% hydrochloric acid, 50 grams and 50 ml./ liter, respectively.
- the solution is allowed to stand for approximately one hour at room temperature, during which time the color will change, starting with blue-black, then dark green and deep brown and finally a dark brown. At this stage it is believed that the solution contains considerable quantities of the catalytically active palladium, stannous chloride complex and requires the addition of an excess of stannous chloride. It is preferred to add 50 grams, although the amount is nominal and more-01 even less-of an excess will do.
- the solution is then diluted with a stannous chloride, hydrochloric acid solution to give a composition having the following concentrations of components:
- the solution will be unstable and a black precipitate will form after standing for several days.
- the black precipitate is believed to contain a palladium, stannous complex and palladium metal.
- the precipitate complex can be redissolved in concentrated hydrochloric acid and will be catalytically active. To achieve stability excess stannous tin should be added to the solution.
- the precipitated palladium metal will not redissolve in the concentrated hydrochloric acid unless an oxidizing agent such as hydrogen peroxide is added.
- a catalytically active solution containing 1 gram/liter of palladium chloride is prepared as described above, but as a stabilizing ingredient, there is added 50 grams/liter of resorcinol.
- the solution can be stabilized with ethylene glycol, 700 ml./liter, or isopropanol, 450 ml. per liter.
- Example 9 An additional dilute solution is prepared in substantially the same manner as hereinabove described, having both a high concentration of the preferred complex, as well as good catalytic activity.
- the dilute solution consists of the following concentrations of components:
- the inactive solution is prepared by dissolving 1 gram of palladium chloride in water containing 200 ml. of 37% hydrochloric acid and then dissolving 80 grams of stannous chloride in the solution.
- the resulting solution is not catalytically active even though a palladium, stannous chloride complex is formed as will be evidenced by the fact that the original palladium chloride, hydrochloric acid solution looses its original properties.
- the palladium chloride, hydrochloric acid solution will have a light yellow color and will galvanically deposit palladium metal on a strip of copper metal.
- the addition of stannous chloride will change the color of the solution to deep green and the solution will no longer galvanically deposit palladium metal on a strip of copper.
- Example 10 A solution is prepared comprising the following ingredients:
- Example 11 A sensitizing solution comprising the following ingreclients is prepared:
- This composition is formulated by dissolving palladium chloride in water containing 40 to 60 ml. of 37% or 1 N hydrochloric acid. Dissolution is slow and continues normally for several hours at room temperature. When the palladium is completely dissolved the stannous chloride is dissolved in the resulting solution. It is noted in this regard that when the stannous chloride is first dissolved in the aforesaid solution a green color may be noticed initially. After about one hour, however, the solu tion will change to a dark brown color, which coloration indicates that the solution, which is made up to 1 liter with water, is ready for use. The panel being prepared for plating is then immersed in the sensitizing solution for a period of from 5 to 20 minutes at room temperature.
- stannous chloride is preferred in the practice of the present invention
- other stannous tin compounds such as, for example, stannous fluoborate and stannous sulfate are also suitable for use in the seeding, i.e., sensitizing compositions described herein and in equivalent concentrations.
- Example 12 The following is an example of a suitable sensitization solution having high acid content:
- Example 13 The following is an exampe of stannous fluoborate compositions which may be used as the sensitizing solution:
- Example 14 The following is an exampe of stannous sulfate compositions which may be used as the sensitizing solution:
- the stannous fiuoroborate and stannous sulfate sesitizing solutions are made up in a manner similar to that described hereinabove in connection with the stannous chloride solutions.
- Example 15 Platinum chloride gram 1 Stannous chloride grams 20 Hydrochloric acid (37%) ml 40 Water, to 1000 ml.
- Example 16 Rhodium chloride grams 4 Stannous chloride grams 20 Hydrochloric acid (37%) ml 40 Water, to 1000 ml.
- Example 17 Palladium chloride gram 1 Acetic acid (99.5%) ml 880 Stannous chloride grams 20 Water, to 1000 ml.
- the panel surfaces including any side walls of the apertures defined therein are thereafter thoroughly rinsed with water to entirely remove the sensitizing solution therefrom.
- the panel is then passed through a further bath of hydrochloric acid, suitably diluted, e.g., about 10 percent, the passage employing a period of from 10 to 20 seconds, and the panel is again rinsed with water prior to immersion in a suitable electroless plating bath.
- electroless plating baths may be used for the deposition of the adherent metal after sensitizing of the plating surface with the compositions of the present invention.
- the electroless copper deposition may be followed by electroplating with copper or other metals to build up copper thicknesses of 0.01 to 0.002 inch or greater.
- electroless copper is ordinarily deposited on apertures formed in plastic insulation sheets which have conductive copper foil laminated on both top and bottom surfaces.
- the circuits are conventionally electroplated with copper or other metals to build up copper thicknesses of 0.001 to 0.002 inch or greater.
- Electroplated copper is required over the electroless copper to form rugged conductive copper on the walls of the aperture approximately 0.001 inch thick or greater.
- the adhesion between the electroless copper and the foil originally laminated to the plastic sheet has been very poor due to a poorly adherent flash coating of precious metal from the catalyzing step.
- the subsequent electrodeposits fail because of the flash coating and could easily be stripped off merely by the application of pressure sensitive adhesive coated cellophane tape such as Scotch cellophane tape manufactured by the Minnesota Mining and Manufacturing Company. Therefore, prior to the advent of the present invention, in order to achieve adherent coating, the surface of the copper foil had to be mechanically abraded before electroplating to remove all trace of the electroless copper deposits. This was a costly and time-consuming operation. By using the sensitizing solutions of the present invention, however, it is not necessary to abrade the surface to remove the electroless copper.
- the electroplated copper may be deposited directly and will adhere so strongly that if the plastic base sheet is broken, the copper foil may be bent back and forth on itself until it breaks but no separation is evident between the original laminated foil and the electroplated copper film.
- a process for the preparation of a concentrated composition dilutable to an optically clear, sensitizer solution for rendering a surface receptive to the deposition of an adherent electroless metal which comprises water and a metal complex consisting essentially of:
- (c) an anion capable of forming a stable moiety with both valence states of the Group IV metal, the molar ratio of components (a) to (b) to (c) being from about 1:123 to 1:6:24, and wherein the concentration of component (a) is at least about 1.5 grams/ liter which comprises heating an aqueous mixture containing said components (a), (b) and (c), in which mixture component (a) is present in a concentration of at least about 1.5 grams/liter, at a temperature of from about C. to about the boiling point of said mixture, until the formation of said metal complex is substantially complete.
- a process for the preparation of a concentrated composition as defined in claim 1 which comprises;
- a stabilized sensitizer solution for rendering a surface receptive to the deposition of an adherent electroless metal consisting of:
- component (C) a compound selected from the group consisting of a fluorinated hydrocarbon wetting agent and hydrogen fiuoride, the amount of said compound in said solution being at least sufficient to prevent separation therefrom of component (a) as a metallic film or precipitate.
- stabilizing ingredient C is selected from the group consisting of a wetting agent characterized by a stable fluorocarbon tail and a solubilizing group and hydrogen fluoride.
- component (b) is tin.
- component (a) is platinum
- component (b) is tin.
- component (c) is Cl, SnCl or a mixture thereof.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US906070A | 1970-02-05 | 1970-02-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3682671A true US3682671A (en) | 1972-08-08 |
Family
ID=21735359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US3682671D Expired - Lifetime US3682671A (en) | 1970-02-05 | 1970-02-05 | Novel precious metal sensitizing solutions |
Country Status (12)
Country | Link |
---|---|
US (1) | US3682671A (fr) |
JP (3) | JPS5237971B1 (fr) |
AT (1) | AT308487B (fr) |
CA (1) | CA931301A (fr) |
CH (1) | CH564094A5 (fr) |
DE (1) | DE2105898C3 (fr) |
DK (1) | DK144919C (fr) |
ES (1) | ES387979A1 (fr) |
FR (1) | FR2078132A5 (fr) |
GB (1) | GB1306201A (fr) |
NL (1) | NL165790C (fr) |
SE (1) | SE427189B (fr) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2350147A1 (de) * | 1973-06-27 | 1975-03-20 | Shipley Co | Katalysator fuer die stromlose metallabscheidung auf einem substrat und verfahren zu seiner verwendung |
US3960573A (en) * | 1972-08-07 | 1976-06-01 | Photocircuits Division Of Kollmorgan Corporation | Novel precious metal sensitizing solutions |
US3961109A (en) * | 1973-08-01 | 1976-06-01 | Photocircuits Division Of Kollmorgen Corporation | Sensitizers and process for electroless metal deposition |
US3963841A (en) * | 1975-01-06 | 1976-06-15 | International Business Machines Corporation | Catalytic surface preparation for electroless plating |
US3993491A (en) * | 1973-12-07 | 1976-11-23 | Surface Technology, Inc. | Electroless plating |
US4004051A (en) * | 1974-02-15 | 1977-01-18 | Crown City Plating Company | Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating |
DE2725096A1 (de) * | 1976-06-28 | 1978-01-05 | Ibm | Verfahren zum praeparieren der oberflaeche eines dielektrischen materials fuer das stromlose aufbringen von metallschichten |
DE2659680A1 (de) * | 1976-12-30 | 1978-07-13 | Ibm Deutschland | Verfahren zum sensibilisieren von oberflaechen |
US4160050A (en) * | 1976-04-13 | 1979-07-03 | Kollmorgen Technologies Corporation | Catalyzation processes for electroless metal deposition |
DE2928699A1 (de) * | 1978-07-25 | 1980-02-07 | Alfachimici Spa | Katalytische loesung zum stromlosen niederschlagen von metallen sowie verfahren fuer ihre herstellung |
US4239538A (en) * | 1976-03-30 | 1980-12-16 | Surface Technology, Inc. | Catalytic primer |
US4259113A (en) * | 1976-05-26 | 1981-03-31 | Kollmorgen Technologies Corporation | Composition for sensitizing articles for metallization |
EP0109402A1 (fr) * | 1982-05-26 | 1984-05-30 | Macdermid Inc | Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique. |
US4592929A (en) * | 1984-02-01 | 1986-06-03 | Shipley Company Inc. | Process for metallizing plastics |
US4610895A (en) * | 1984-02-01 | 1986-09-09 | Shipley Company Inc. | Process for metallizing plastics |
US4662944A (en) * | 1972-07-11 | 1987-05-05 | Kollmorgen Technologies Corporation | Process and composition for sensitizing articles for metallization |
US4717421A (en) * | 1986-04-28 | 1988-01-05 | Mcgean-Rohco, Inc. | Solid tin-palladium catalyst for electroless deposition incorporating stannous salts of organic acids |
DE3928500A1 (de) * | 1989-08-29 | 1991-03-14 | Deutsche Automobilgesellsch | Verfahren zum waschen und spuelen chemisch metallisierter substratbahnen |
US5089301A (en) * | 1988-12-24 | 1992-02-18 | Mercedes-Benz Ag | Solution for the activating of electrically nonconductive substrate surfaces and method of preparing the said solution |
US5292557A (en) * | 1992-11-16 | 1994-03-08 | Allied-Signal Inc. | Electroless plating of substrates |
EP0616053A1 (fr) | 1993-03-18 | 1994-09-21 | Atotech Usa, Inc. | Bain de revêtement par immersion sans formaldéhyde, auto-accélérant et auto-rajeunissant, méthode et composition |
US5418064A (en) * | 1992-11-16 | 1995-05-23 | Allied Signal Inc. | Electroless plating of substrates |
US5753304A (en) * | 1997-06-23 | 1998-05-19 | The Metal Arts Company, Inc. | Activation bath for electroless nickel plating |
US6261637B1 (en) * | 1995-12-15 | 2001-07-17 | Enthone-Omi, Inc. | Use of palladium immersion deposition to selectively initiate electroless plating on Ti and W alloys for wafer fabrication |
EP1988192A1 (fr) | 2007-05-03 | 2008-11-05 | Atotech Deutschland Gmbh | Procédé d'application d'un revêtement métallique sur un substrat non conducteur |
WO2011035921A1 (fr) | 2009-09-28 | 2011-03-31 | Atotech Deutschland Gmbh | Procédé d'application de revêtement métallique sur un substrat non conducteur |
US20120171363A1 (en) * | 2009-09-11 | 2012-07-05 | C. Uyemura & Co., Ltd. | Catalyst application solution, electroless plating method using same, and direct plating method |
EP2767614A1 (fr) | 2013-02-13 | 2014-08-20 | ATOTECH Deutschland GmbH | Procédé pour déposer une première couche métallique sur des polymères non conducteurs |
US9932676B2 (en) * | 2014-07-17 | 2018-04-03 | Electroplating Engineers Of Japan Limited | Pretreatment solution for electroless plating and electroless plating method |
CZ309565B6 (cs) * | 2022-02-02 | 2023-04-12 | EGO 93 s.r.o | Senzibilační roztok a způsob jeho přípravy |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1021761A (fr) * | 1973-08-01 | 1977-11-29 | Kollmorgen Corporation | Sensibilisateurs pour depot chimique des metaux |
ZA774561B (en) * | 1976-09-20 | 1978-06-28 | Kollmorgen Tech Corp | Preparation of solid precious metal sensitizing compositions |
DE3323476A1 (de) * | 1982-07-01 | 1984-01-05 | Kollmorgen Technologies Corp., 75201 Dallas, Tex. | Verbessertes verfahren zur galvanischen metallabscheidung auf nichtmetallischen oberflaechen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
DE1446224B2 (de) * | 1960-09-01 | 1971-09-16 | Photocircuits Corp , Glen Cove, NY (V St A ) | Saure waessrige loesung zum sensibilisieren von oberflaechen zur anschliessenden stromlosen metallabscheidung |
GB1174851A (en) * | 1967-07-05 | 1969-12-17 | Technograph Ltd | Sensitization Process for Electroless Plating |
-
1970
- 1970-02-05 US US3682671D patent/US3682671A/en not_active Expired - Lifetime
- 1970-09-02 CA CA092191A patent/CA931301A/en not_active Expired
- 1970-09-25 JP JP8458070A patent/JPS5237971B1/ja active Pending
-
1971
- 1971-01-18 GB GB232771A patent/GB1306201A/en not_active Expired
- 1971-02-01 AT AT81871A patent/AT308487B/de active
- 1971-02-01 SE SE119871A patent/SE427189B/xx unknown
- 1971-02-01 CH CH142671A patent/CH564094A5/xx not_active IP Right Cessation
- 1971-02-03 FR FR7103580A patent/FR2078132A5/fr not_active Expired
- 1971-02-04 DK DK48471A patent/DK144919C/da not_active IP Right Cessation
- 1971-02-04 DE DE2105898A patent/DE2105898C3/de not_active Expired
- 1971-02-05 NL NL7101596A patent/NL165790C/xx not_active IP Right Cessation
- 1971-02-05 ES ES387979A patent/ES387979A1/es not_active Expired
-
1974
- 1974-01-11 JP JP696174A patent/JPS5373429A/ja active Pending
- 1974-01-11 JP JP696074A patent/JPS5426495B1/ja active Pending
Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4662944A (en) * | 1972-07-11 | 1987-05-05 | Kollmorgen Technologies Corporation | Process and composition for sensitizing articles for metallization |
US3960573A (en) * | 1972-08-07 | 1976-06-01 | Photocircuits Division Of Kollmorgan Corporation | Novel precious metal sensitizing solutions |
DE2350147A1 (de) * | 1973-06-27 | 1975-03-20 | Shipley Co | Katalysator fuer die stromlose metallabscheidung auf einem substrat und verfahren zu seiner verwendung |
US3961109A (en) * | 1973-08-01 | 1976-06-01 | Photocircuits Division Of Kollmorgen Corporation | Sensitizers and process for electroless metal deposition |
US3993491A (en) * | 1973-12-07 | 1976-11-23 | Surface Technology, Inc. | Electroless plating |
US4004051A (en) * | 1974-02-15 | 1977-01-18 | Crown City Plating Company | Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating |
US3963841A (en) * | 1975-01-06 | 1976-06-15 | International Business Machines Corporation | Catalytic surface preparation for electroless plating |
US4239538A (en) * | 1976-03-30 | 1980-12-16 | Surface Technology, Inc. | Catalytic primer |
US4160050A (en) * | 1976-04-13 | 1979-07-03 | Kollmorgen Technologies Corporation | Catalyzation processes for electroless metal deposition |
US4259113A (en) * | 1976-05-26 | 1981-03-31 | Kollmorgen Technologies Corporation | Composition for sensitizing articles for metallization |
DE2725096A1 (de) * | 1976-06-28 | 1978-01-05 | Ibm | Verfahren zum praeparieren der oberflaeche eines dielektrischen materials fuer das stromlose aufbringen von metallschichten |
DE2659680A1 (de) * | 1976-12-30 | 1978-07-13 | Ibm Deutschland | Verfahren zum sensibilisieren von oberflaechen |
DE2928699A1 (de) * | 1978-07-25 | 1980-02-07 | Alfachimici Spa | Katalytische loesung zum stromlosen niederschlagen von metallen sowie verfahren fuer ihre herstellung |
US4244739A (en) * | 1978-07-25 | 1981-01-13 | Roberto Cagnassi | Catalytic solution for the electroless deposition of metals |
EP0109402A1 (fr) * | 1982-05-26 | 1984-05-30 | Macdermid Inc | Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique. |
EP0109402A4 (fr) * | 1982-05-26 | 1984-10-29 | Macdermid Inc | Solutions catalytiques permettant d'activer des substrats non conducteurs et procede de placage sans passage de courant electrique. |
US4592929A (en) * | 1984-02-01 | 1986-06-03 | Shipley Company Inc. | Process for metallizing plastics |
US4610895A (en) * | 1984-02-01 | 1986-09-09 | Shipley Company Inc. | Process for metallizing plastics |
US4717421A (en) * | 1986-04-28 | 1988-01-05 | Mcgean-Rohco, Inc. | Solid tin-palladium catalyst for electroless deposition incorporating stannous salts of organic acids |
US5089301A (en) * | 1988-12-24 | 1992-02-18 | Mercedes-Benz Ag | Solution for the activating of electrically nonconductive substrate surfaces and method of preparing the said solution |
DE3928500A1 (de) * | 1989-08-29 | 1991-03-14 | Deutsche Automobilgesellsch | Verfahren zum waschen und spuelen chemisch metallisierter substratbahnen |
US5292557A (en) * | 1992-11-16 | 1994-03-08 | Allied-Signal Inc. | Electroless plating of substrates |
US5418064A (en) * | 1992-11-16 | 1995-05-23 | Allied Signal Inc. | Electroless plating of substrates |
EP0616053A1 (fr) | 1993-03-18 | 1994-09-21 | Atotech Usa, Inc. | Bain de revêtement par immersion sans formaldéhyde, auto-accélérant et auto-rajeunissant, méthode et composition |
US5543182A (en) * | 1993-03-18 | 1996-08-06 | Atotech Usa, Inc. | Self-accelerating and replenishing non-formaldehyde immersion coating method |
US5725640A (en) * | 1993-03-18 | 1998-03-10 | Atotech Usa, Inc. | Composition and process for treating a surface coated with a self-accelerating and replenishing non-formaldehyde immersion coating |
US6261637B1 (en) * | 1995-12-15 | 2001-07-17 | Enthone-Omi, Inc. | Use of palladium immersion deposition to selectively initiate electroless plating on Ti and W alloys for wafer fabrication |
US5753304A (en) * | 1997-06-23 | 1998-05-19 | The Metal Arts Company, Inc. | Activation bath for electroless nickel plating |
US20100119713A1 (en) * | 2007-05-03 | 2010-05-13 | Atotech Deutschland Gmbh | Process for applying a metal coating to a non-conductive substrate |
EP1988192A1 (fr) | 2007-05-03 | 2008-11-05 | Atotech Deutschland Gmbh | Procédé d'application d'un revêtement métallique sur un substrat non conducteur |
US8152914B2 (en) | 2007-05-03 | 2012-04-10 | Atotech Deutschland Gmbh | Process for applying a metal coating to a non-conductive substrate |
US20120171363A1 (en) * | 2009-09-11 | 2012-07-05 | C. Uyemura & Co., Ltd. | Catalyst application solution, electroless plating method using same, and direct plating method |
US8828131B2 (en) * | 2009-09-11 | 2014-09-09 | C. Uyemura & Co., Ltd. | Catalyst application solution, electroless plating method using same, and direct plating method |
WO2011035921A1 (fr) | 2009-09-28 | 2011-03-31 | Atotech Deutschland Gmbh | Procédé d'application de revêtement métallique sur un substrat non conducteur |
EP2305856A1 (fr) | 2009-09-28 | 2011-04-06 | ATOTECH Deutschland GmbH | Processus d'application d'un revêtement métallique sur un substrat non conducteur |
EP2767614A1 (fr) | 2013-02-13 | 2014-08-20 | ATOTECH Deutschland GmbH | Procédé pour déposer une première couche métallique sur des polymères non conducteurs |
WO2014124773A2 (fr) | 2013-02-13 | 2014-08-21 | Atotech Deutschland Gmbh | Procédé de dépôt d'une première couche métallique sur des polymères non conducteurs |
US9932676B2 (en) * | 2014-07-17 | 2018-04-03 | Electroplating Engineers Of Japan Limited | Pretreatment solution for electroless plating and electroless plating method |
CZ309565B6 (cs) * | 2022-02-02 | 2023-04-12 | EGO 93 s.r.o | Senzibilační roztok a způsob jeho přípravy |
Also Published As
Publication number | Publication date |
---|---|
ES387979A1 (es) | 1973-06-01 |
NL165790B (nl) | 1980-12-15 |
AT308487B (de) | 1973-07-10 |
SE427189B (sv) | 1983-03-14 |
JPS5426495B1 (fr) | 1979-09-04 |
NL7101596A (fr) | 1971-08-09 |
DK144919B (da) | 1982-07-05 |
DE2105898A1 (de) | 1971-09-02 |
FR2078132A5 (fr) | 1971-11-05 |
GB1306201A (fr) | 1973-02-07 |
NL165790C (nl) | 1981-05-15 |
JPS5237971B1 (fr) | 1977-09-26 |
DE2105898C3 (de) | 1982-08-19 |
DE2105898B2 (de) | 1975-07-31 |
JPS5373429A (en) | 1978-06-29 |
CH564094A5 (fr) | 1975-07-15 |
CA931301A (en) | 1973-08-07 |
DK144919C (da) | 1982-11-22 |
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