Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—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
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
  • C23C18/1886—Multistep pretreatment
  • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
• • 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
  • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

• the present invention relates to formation of a plating layer in an electroless plating process in the presence of a conductive metal oxide in addition to a metal micropowder. More specifically, the present invention relates to an electroless plating process for forming effectively a uniform plating film resorting to a synergistic effect to be brought about by a conductive metal oxide and a reduction catalyst metal such as palladium which are contained in a coating film of a pretreating agent (or solution or primer).
• plating layers can be formed by electroless plating on nonconductive plastics, ceramics, paper, glass, fibers, etc., it is necessary to apply or immobilize catalysts onto the surfaces of these nonconductive materials so as to initiate oxidation of a reducing agent contained in a plating solution.
• sensitizing-activating method using a stannous chloride bath and a palladium chloride bath is classically known as a technique of catalyst application or immobilization treatment
• catalyst accelerator method using a stannous chloride-palladium chloride bath and a sulfuric acid (or hydrochloric acid) bath is now employed generally.
• a material to be treated is dipped in a palladium complex solution having high adsorptivity, and the resulting material is rinsed with water, followed by deposition of palladium using a reducing agent such as dimethylamine borane.
• An etching step is necessary as a pretreatment to be applied prior to the catalyst application treatment step so as to secure wettability (hydrophilicity) on the surface of the material to be treated and accelerate physical adsorption of the catalyst, and chromic acid-based etching solutions are used in most cases for overall plating of plastics and the like.
• a chemical etching step is very important in order to achieve microscopic roughening of the surfaces of materials to be treated, to facilitate physical capture of the catalyst metal in the catalyst application (immobilization) treatment step and to give an anchoring effect which influences adherence of the plating layers to the materials to be treated.
• the conductive coating method involves problems in terms of cost and weight due to the great thickness of the coating film. Meanwhile, physical adsorption of catalyst metals is an unstable element in the SSP process. Although the Omura Marine process is an epoch-making technique utilizing specific chemical adsorption of catalyst metals, poor solubility in solvents and hygroscopicity of chitosan give adverse influences on coating of metal catalysts.
• the present invention provides a method for applying a catalyst in an electroless plating process.
• the catalyst application which is carried out prior to the electroless plating step, is characterized in that, before carrying out an electroless plating step, a film containing a conductive metal oxide is formed on the surface of a nonconductive material, and the film is treated with a catalyst metal salt solution, i.e., reductive deposition of the target metal ion is induced by electrons of the conductive metal oxide which is stable to acids and alkalis.
• the conductive metal oxide induces, based on its conductivity, a synergistic reducing action to enable formation of an electroless plating film speedily and uniformly on the surface of the nonconductive material compared with the prior art methods.
• nonconductive material referred to in the present invention can be exemplified by plastics, ceramics, paper, glass, fibers, etc. which cannot be plated directly by electroplating.
• a treating solution containing a conductive metal oxide is applied over the surface of the nonconductive material to form a conductive film thereon, prior to the catalyst application step and the electroless plating step.
• the thus formed film accelerates deposition of the target metal ion owing to the conductivity of the conductive metal oxide in the presence of a catalyst metal such as palladium.
• a catalyst metal such as palladium.
• the conductive metal oxide may not particularly be limited so long as it has electronic conductivity and ionic conductivity. It typically includes, for example, M 2 O compounds such as Cu 2 O and Ag 2 O; MO compounds such as SrO, TiO, VO, MnO, FeO, CoO, NiO, CuO, ZnO, NbO, PdO, AgO, CdO and PtO; M 3 O 4 compounds such as Mn 3 O 4 , Fe 3 O 4 and Co 3 O 4 ; M 2 O 3 compounds such as Y 2 O 3 , Ti 2 O 3 , V 2 O 3 , Cr 2 O 3 , Mn 2 O 3 , Fe 2 O 3 , Ga 2 O 3 , Rh 2 O 3 , In 2 O 3 and B-Al 2 O 3 ; MO 2 compounds such as TiO 2 , VO 2 , CrO 2 , MnO 2 , RuO 2 , RnO 2 , NbO 2 , MoO 2 , SnO 2 , WO 2 ,
• TiO 2 , SnO 2 , V 2 O 3 , Ti 2 O 3 , Ga 2 O 3 , In 2 O 3 , Nb 2 O 5 and VO 2 are preferred.
• tin oxide-based conductive metal oxides and indium oxide-based conductive metal oxides doped with antimony and the like and tin respectively so as to reduce resistance are also useful.
• the conductive metal oxides may have a colloidal form or a powdery form having effectively a particle diameter in the range of 0.001 to 40 ⁇ m, preferably in the range of 0.01 to 20 ⁇ m.
• the treating solution containing a conductive metal oxide desirably contains the conductive metal oxide in an amount of 5 to 70 mass %, preferably in an amount of 10 to 45 mass % in terms of the metal oxide.
• the effect to be brought about by adding the conductive metal oxide diminishes as the amount of the metal oxide becomes smaller than 5 mass %, making it difficult to form a conductive layer necessary for formation of a plating layer. Meanwhile, if the conductive metal oxide is added in an amount of more than 70 mass %, the effect to be brought about by the addition thereof is saturated, and adherence of the plating layer is lowered.
• a resin binder having excellent adherence to materials to be plated can be added.
• the resin to be added may not particularly be limited so long as it disperses well in the conductive metal oxide or is miscible therewith.
• Binders employable here include, for example, solvent-evaporation type (thermoplastic or thermosetting) resins such as nitrocellulose, cellulose acetate, acrylic, epoxy and phenol resins; crosslinking reaction type resins such as urethane, acrylic urethane, epoxy, polyester and epoxy polyester resins.
• a water-soluble resin such as polyvinyl alcohols and hydroxyethyl celluloses
• a hydrated resin such as of alkyd, polyester, acrylic or epoxy
• an emulsion such as of vinyl acetate resin, acrylic resin, urethane resin, silicone acrylic resin or fluororesin
• amino-containing polymers such as collagen, polyglutamic acids, chondroitin sulfuric acid, hyaluronic acid, chitosan, chitosan derivatives, polyethyleneimines and polyallylamines may be added singly or as a combination of two or more of them to achieve much firmer adsorption and immobilization of the reduction catalyst.
• Particularly chitosan and chitosan derivatives are preferred among other polymers. These compounds are usually contained, depending on the kind thereof, in an amount of 5 to 85 mass %, preferably 15 to 70 mass % in the solid content including the conductive metal oxide.
• various kinds of metal micropowders, inorganic pigments, metal oxides, carbonic salt compounds, phosphoric salt compounds, etc. are as necessary added. That is, such substances are added to achieve microscopic roughening of the surface of the film that contributes further to improvement of adherence of the plating layer, in forming an electroless plating layer, resorting to the conductivity, anchoring effect or metal ion adsorbing effect. This can be a substitute for the chemical etching step and catalyst application step in the prior art.
• microparticulate powders of, for example, gold, platinum, palladium, silver, steel, nickel, graphite, nickel-plated graphite and carbon; as well as, silica, calcium silicate, iron silicate, aluminum silicate, magnesium silicate, calcium magnesium silicate, aluminum oxide, magnesium oxide, magnesium aluminate silicate, calcium aluminate silicate, barium aluminate silicate, beryllium aluminate silicate, strontium aluminate silicate, titanium oxide, calcium carbonate, barium sulfate, zinc phosphate, aluminum tertiary phosphate, aluminum secondary phosphate, aluminum primary phosphate, calcium tertiary phosphate, calcium secondary phosphate, calcium primary phosphate, cobalt phosphate, zirconyl phosphate, titanium phosphate, nickel phosphate, bismuth phosphate, magnesium tertiary phosphate, magnesium secondary phosphate, manganese secondary phosphate, manganese, manganese secondary
• magnesium aluminate silicate is preferred.
• Such materials are usually added in an amount of 5 to 85 mass %, preferably 20 to 70 mass % in the solid content including the conductive metal oxide. If the content of such material is more than 85 wt %, the adhesion between the conductive metal oxide-containing treating agent and the material to be plated itself is lowered.
• Other components to be contained in the treating solution include an organic solvent such as methanol, isopropyl alcohol, n-butanol, isobutanol, ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, xylene, glycol ether, tetrahydrofuran, n-hexane, mineral terpene and glycol ether, and water.
• organic solvent such as methanol, isopropyl alcohol, n-butanol, isobutanol, ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, xylene, glycol ether, tetrahydrofuran, n-hexane, mineral terpene and glycol ether, and water.
• organic solvent such as methanol, isopropyl alcohol, n-butanol, isobutanol,
• the treating solution may as necessary be incorporated with additives such as a surface controlling agent, an antiprecipitant, a dispersant, a defoaming agent and an aminosilane coupling agent, and these additives can impart appropriately leveling properties, pigment dispersibility, metal adsorbing action, hydrophilicity, etc. to the treating solution in film formation.
• additives such as a surface controlling agent, an antiprecipitant, a dispersant, a defoaming agent and an aminosilane coupling agent, and these additives can impart appropriately leveling properties, pigment dispersibility, metal adsorbing action, hydrophilicity, etc.
• the conductive metal oxide-containing treating solution as described above can be applied to the surface of a material to be plated according to the conventional coating techniques, for example, spray coating, roll coating, brush coating and dipping and forms a film for immobilizing a catalyst metal thereon showing excellent adherence against the material to be plated.
• the step of capturing and immobilizing a catalyst metal as a catalyst imparting reaction and the step of electroless plating are carried out successively, and thus an electroless plating layer having excellent adherence can be formed efficiently.
• the surface of the nonconductive material may partly be pretreated with a treating solution containing a conductive metal oxide to impart reductive catalysis selectively to such pretreated portions, thus achieving secured partial electroless plating.
• electroless plating can be applied well to polyester resins such as polyethylene terephthalate; 6,6-nylon, 6-nylon, polyolefins, polycarbonates; various kinds of alloys such as PC/ABS and PC/ASA; carbon fiber or glass fiber-reinforced alloys, which have been difficult to form electroless plating layers thereon.
• polyester resins such as polyethylene terephthalate; 6,6-nylon, 6-nylon, polyolefins, polycarbonates; various kinds of alloys such as PC/ABS and PC/ASA; carbon fiber or glass fiber-reinforced alloys, which have been difficult to form electroless plating layers thereon.
• a reduction catalyst is preferably carried out by dipping for a short period the material to be plated, for example, in an acidic solution of a hydrochloride, nitrate or acetate of a noble metal such as Pd, Pt, Au and Ag in hydrochloric acid, nitric acid or acetic acid.
• a palladium chloride solution (0.2 to 1 g/L, hydrochloric acid 5 ml/L) as employed in the conventional method can be used.
• the above catalyst application step can be omitted.
• the material to be plated carrying the catalyst metal in the conductive metal oxide-containing film is dipped in an electroless plating bath such as of Cu, Ni, Co, Pd or Au, or an alloy thereof, preferably of Cu or Ni, and thus an electroless plating layer having excellent adherence can be obtained continuously and efficiently based on the conductivity of the conductive metal oxide or on the interaction between the conductive metal oxide and the immobilized reduction catalyst, thus achieving desired metallization of the nonconductive material.
• an electroless plating bath such as of Cu, Ni, Co, Pd or Au, or an alloy thereof, preferably of Cu or Ni
• the metal ion concentration in the plating bath can be adjusted in a wide range. However, a too low concentration causes film formation to proceed at an extremely low speed, whereas a too high concentration causes precipitation of the metal ion or deterioration of plating films to be formed.
• the metal ion concentration is preferably 0.001 to 5 mol/L, particularly preferably 0.01 to 0.5 mol/L.
• the temperature of the plating solution is not particularly limited, it is preferably 10 to 95°C. A too low temperature causes film formation to proceed at a low speed, whereas a decomposition reaction of a reducing catalyst is likely to proceed at a too high temperature.
• the pH of the plating solution is not particularly limited, it is preferably about 3 to 13. If the pH is lower then the specified range, the film formation speed is lowered, whereas if it is higher than the range, the plating solution becomes unstable to be likely to undergo autolysis.
• a conventional buffer can be added to the bath so as to maintain a predetermined level of pH stably.
• the buffer can be exemplified by potassium dihydrogenphosphate, potassium phthalate and borax.
• Stirring techniques employable include, for example, bubbling with air, nitrogen, oxygen, etc.; cathode lock method where a material to be plated is moved; paddling where a rod-like stirring mechanism is moved in the vicinity of a material to be plated; a method using an ultrasonic wave, particularly a superimposed ultrasonic wave formed by superimposing ultrasonic waves with different frequencies (e.g., a hybrid of three waves, 28 kHz, 45 kHz and 100 kHz); a method where the frequency is changed with lapse of time; or a method using a highfrequency ultrasonic wave having a frequency of as high as around 1 GHz.
• frequencies e.g., a hybrid of three waves, 28 kHz, 45 kHz and 100 kHz
• Film formation can be achieved by charging such plating solution in a plating tank provided with a predetermined heater and a filter device and dipping a base material therein.
• the plating solutions in these cases are preferably filtered through ca. 0.2 ⁇ m-mesh filters and the like before recycling.
• a PET film (6 cm ⁇ 12 cm) was coated with a treating solution (Yamanaka Chemical Co., Ltd.) having a sol of amorphous colloidal stannic oxide suspended together with an acrylic ester copolymer using a bar coater No. 8, and the resulting coating layer was then subjected to forced drying at 110°C for 3 minutes. After the thus treated PET film was left to stand at 23°C ⁇ 50 % RH for 24 hours, the surface electrical resistance of the film was measured using a resistor SM-5E (Toa Electronics Ltd.), and it was found to be 8.6 ⁇ 10 6 ⁇ . The thickness of the primer formed was 0.3 ⁇ m.
• the resulting PET film was dipped in a palladium chloride solution (PdCl 2 ⁇ 2H 2 O: 0.2 g/L; hydrochloric acid: 5 ml/L) for one minute, rinsed with water and then subjected to electroless copper plating for 30 minutes in a plating bath having the composition as shown in Table 1.
• a copper plating layer having excellent luster was formed on the portion coated with the treating solution.
• ACRYDIC A-166 one-component type room temperature-drying acrylic lacquer, Dainippon Ink & Chemicals, Ltd.
• stannic oxide first class grade chemical; Wako Pure Chemical Ind., Ltd.
• Disperbyk-180 solvent type wetting and dispersing agent, BYK-Chemie GmbH
• the resulting ABS resin piece was subjected successively to plating in an electroless copper plating bath for 30 minutes and electroless nickel plating for 5 minutes using a bath composition as shown in Table 2.
• a uniform copper/nickel plating layer having a copper plating film thickness of 0.8 to 1.2 ⁇ m and a nickel film thickness of 0.3 to 0.8 ⁇ m was obtained.
• the glass beads were filtered off, and the filtrate mixture was obtained as a pretreating stock solution.
• An ABS resin piece (50 mm ⁇ 150 mm ⁇ 1 mm; Ube Cycon, Ltd.) was taken as a material to be plated. After the resin piece was degreased with n-heptane, a solution obtained by diluting twice the pretreating stock solution with a mixed solvent of butyl acetate/ethyl acetate/n-butanol/toluene/ethyl cellosolve (20:25:20:20:15) was applied thereto by means of spraying and dried at 60°C for one hour.
• the resin piece After treatment of the surface of the thus treated ABS resin piece with an alkali, the resin piece was dipped in a palladium chloride solution (PdCl 2 ⁇ 2H 2 O: 0.2 g/L; hydrochloric acid: 5 ml/L) for 3 minutes, rinsed with water and then reduced with a 1% DMAB solution. Subsequently, the resulting ABS resin piece was subjected successively to plating for 45 minutes in an electroless copper plating bath as shown in Table 1 and electroless nickel plating for 5 minutes using a bath composition as shown in Table 2. As a result, a uniform copper/nickel plating layer having a copper plating film thickness of 0.7 to 1.5 ⁇ m and a nickel film thickness of 0.3 to 0.8 ⁇ m was obtained.
• a palladium chloride solution PdCl 2 ⁇ 2H 2 O: 0.2 g/L; hydrochloric acid: 5 ml/L
• dispersing discs 100 mm-diameter disc ⁇ 4
• 850 g of glass beads for dispersing white paints were introduced thereto to effect dispersion of the resulting mixture for 30 minutes at a medium speed.
• the glass beads were filtered off, and to the filtrate mixture was added the residual liquid in the stainless steel vessel washed with 70 g of butyl acetate/PGM (2:1) to provide a pretreating stock solution.
• Resin pieces of an ABS resin (TM-20, Mitsubishi Rayon Company Limited), PC (FIN-5000R, Mitsubishi Engineering Plastics Corporation), PC/ABS (T-3011, Teijin Chemicals Ltd.), PC/GF 10 % (SP-7602, General Electric Japan, Ltd.), Nylon 6 (PAMXD6, Mitsubishi Engineering Plastics Corporation) were taken as materials to be plated.
• the resin piece After treatment of the surface of the thus treated resin piece with an alkali, the resin piece was dipped in a palladium chloride solution (PdCl 2 ⁇ 2H 2 O: 0.2 g/L; hydrochloric acid: 5 ml/L) at 30°C for 3 minutes, rinsed with water and then reduced with a 1% DMAB solution. Subsequently, the resulting resin piece was subjected successively to plating for 30 minutes in an electroless copper plating bath as shown in Table 1 and electroless nickel plating for 5 minutes using a bath composition as shown in Table 2.
• a palladium chloride solution PdCl 2 ⁇ 2H 2 O: 0.2 g/L; hydrochloric acid: 5 ml/L
• thermo-hygrostat PR-1ST Teabi Espec Corp.
• Test plate Mitsubishi Rayon Company Limited., ABS TM-20, HB type
• Test plate Mitsubishi Engineering Plastics Corporation, PC FIN-5000R, V0 type
• Test plate Teijin Chemicals Ltd., PC/ABS T-3011, HB type
• Test plate General Electric Japan, Ltd., PC/GF 10%, SP-7602, V0 type
• Test plate Mitsubishi Engineering Plastics Corporation, PAMXD 6, HB type
• the copper/nickel plating layers obtained each showed substantially no gain in the electrical resistance values in various environmental tests, and no secondary adhesion occurred.
• the present invention can provide an absolutely novel electroless plating process including a step of applying a pretreating solution containing a conductive metal oxide to a material to be treated before application of a catalyst thereto, which process gives less environmental impact, which is less expensive, and which can achieve more efficient and secured reductive deposition of a metal contained in a plating solution.

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• 2000
  • 2000-03-27 JP JP2000087406A patent/JP2001271171A/ja active Pending
  • 2000-09-12 EP EP00307877A patent/EP1148153A2/fr not_active Withdrawn
  • 2000-10-11 KR KR1020000059687A patent/KR20010089839A/ko not_active Application Discontinuation
  • 2000-11-28 CN CN00128384A patent/CN1315589A/zh active Pending

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