WO2018079188A1 - Procédé de type traitement thermique destiné à la formation d'un revêtement électroconducteur sur un métal léger formant un état passif - Google Patents

Procédé de type traitement thermique destiné à la formation d'un revêtement électroconducteur sur un métal léger formant un état passif Download PDF

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WO2018079188A1
WO2018079188A1 PCT/JP2017/035477 JP2017035477W WO2018079188A1 WO 2018079188 A1 WO2018079188 A1 WO 2018079188A1 JP 2017035477 W JP2017035477 W JP 2017035477W WO 2018079188 A1 WO2018079188 A1 WO 2018079188A1
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film
nickel
acid
forming
conductive
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PCT/JP2017/035477
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English (en)
Japanese (ja)
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藤原　雅宏
山本　和志
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石原ケミカル株式会社
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Priority to KR1020197011955A priority Critical patent/KR20190057105A/ko
Priority to CN201780066043.1A priority patent/CN109891004B/zh
Priority to KR1020217011088A priority patent/KR102409545B1/ko
Publication of WO2018079188A1 publication Critical patent/WO2018079188A1/fr

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    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C18/31—Coating with metals
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting

Definitions

  • the present invention relates to a method for forming a conductive film on a specific light metal such as aluminum or magnesium that easily forms a nonconductive state.
  • the present invention provides a method by which a conductive film such as copper, silver, tin or the like can be formed with strong adhesion on the light metal, which is difficult to form a plating film, by applying heat treatment.
  • a conductive film such as copper, silver, or tin is applied to the surface of these light metals. Even if it is to be formed, surface treatment by plating or the like is difficult. Moreover, even if a plating film can be formed, it is difficult to ensure good adhesion with the light metal. Therefore, conventionally, a conductive film is formed by electroplating after the light metal is surface-treated by a double zincate method, an anodic oxidation method, an inversion electrolytic activation method, or the like.
  • a conductive film on a light metal that easily forms a non-conductive state such as aluminum or magnesium conventionally, the surface is subjected to alkali degreasing and the like to form a nickel-based film, or a predetermined amount of After the surface treatment using the treatment liquid, a conductive film such as copper, silver or tin was formed.
  • the conventional technology is as follows.
  • Patent Document 6 below focuses on forming a nickel-based film on the light metal itself.
  • Patent Document 1 Aluminum or aluminum alloy is subjected to AC electrolytic treatment in a treatment bath containing phosphoric acid and a prescribed nickel salt (nickel carbonate, nickel citrate, etc.) to form an oxide film with a fine concavo-convex structure and electroanalysis of particulate nickel
  • a method for plating an aluminum material comprising a first step of simultaneously performing extraction and a second step of performing electroless or electrolytic plating of copper, nickel or the like thereafter (claim 1, [0014] to [0015] [0044]).
  • nickel metal enters the inside of the oxide film to form an anodic oxide film having a certain thickness, and then the surface is uniformly coated with the particulate nickel film ([0014]).
  • Example 5 [0031] of the treatment liquid in the first step, a nickel salt, phosphoric acid, and malonic acid (dicarboxylic acid) are included.
  • Example 8 nickel citrate and , And phosphoric acid.
  • Patent Document 2 For the purpose of preventing cracks on the plating film ([0008]), after the oxide film on the aluminum or aluminum alloy is removed acidic or alkaline ([0009] to [0026]), the first electroless nickel-phosphorous plating A method for surface treatment of an aluminum material comprising a step of forming an electroless plating film with a liquid and a step of forming an electroless plating film with a second electroless nickel-phosphorous plating liquid (Claim 1, [0009]). . Through this treatment method, a conductive film is formed.
  • the first electroless nickel-phosphorous plating solution includes a nickel salt, hypophosphorous acid or a salt thereof, and a carboxylic acid other than aminocarboxylic acid (citric acid, acetic acid, succinic acid, malic acid, salts thereof ([0036
  • the second electroless nickel-phosphorous plating solution comprises a nickel salt, hypophosphorous acid or a salt thereof, and aminocarboxylic acid (glycine, alanine, leucine, aspartic acid, glutamic acid) or a salt thereof. Contains no carboxylic acids other than aminocarboxylic acids.
  • Example 1 a silicon plate coated with an aluminum layer was subjected to two-stage electroless nickel-phosphorus plating, and then a gold film was coated by electroless plating (Table 1).
  • Patent Document 3 Pretreatment by cathode activation in a pretreatment liquid containing sulfuric acid and a nickel salt (or iron salt, cobalt salt) on at least one surface of an aluminum or aluminum alloy molded article; A surface treatment method comprising a step of applying a metal layer (nickel, iron, cobalt and alloys thereof) to the material by electroplating (claims 1 and 2).
  • a nickel nucleus is formed through a thin aluminum oxide film on the surface of the aluminum material.
  • the nickel nucleus serves as an anchor point. It plays the role of a thin bonding layer that connects ([0012]).
  • boric acid is mentioned as a preferable example of the buffering agent contained in the pretreatment liquid used for the cathode activation treatment (claims 3 to 4, [0013]).
  • Patent Document 4 Before forming a copper plating layer on the magnesium alloy by using electrolytic plating, the surface of the magnesium alloy is treated with a pretreatment solution containing zinc sulfate, sodium pyrophosphate, potassium fluoride, and sodium carbonate to obtain a uniform current distribution.
  • This is a method of forming a film for electroplating with a surface of a magnesium alloy (claims 1 and 2).
  • the electroplating film 1 formed on the surface of the magnesium alloy is easily bonded to the copper plating layer, and the electrocopper plating layer 1 having good adhesion is formed ([0017], [0020] to [0021]). ).
  • Patent Document 5 A surface treatment of Al or Al alloy (Al alloy, etc.) by cathodic electrolysis in a phosphoric acid solution, and electroplating the surface-treated Al alloy, etc. to form a nickel film, nickel- Forming a plating film selected from a phosphorous film or a nickel-phosphorous-silicon carbide alloy film (claims 1 to 3).
  • Cathodic electrolytic treatment of Al alloy or the like in a phosphoric acid solution reduces or removes metal components such as magnesium, iron, and nickel other than Al and silicon, and etches the surface of Al alloy and the like to form fine irregularities. Due to the anchor effect, the plating film can be coated on the surface of an Al alloy or the like with good adhesion ([0016] to [0017], [0029] to [0032]).
  • Patent Document 6 In a developing roller such as a copying machine, an electro nickel plating layer is formed on an aluminum alloy sleeve constituting the developing roller, or an electro nickel plating layer is formed through an electroless nickel plating layer, and thereafter This is a method for improving the adhesion strength of the plating layer to the aluminum alloy layer by performing heat treatment (claims 1 to 4, [0010], [0018] to [0019]). The heat treatment is performed at 100 ° C. to 150 ° C. for 30 minutes to 2 hours ([0015]).
  • Patent Documents 1 to 5 or a process based on the process is performed on a light metal such as aluminum or magnesium, which is easy to form a nonconductive state, via a nickel-based undercoat or before.
  • a nickel-phosphorous film may be formed by electroless plating. The adhesion of the electroless nickel-phosphorus film to the light metal surface is weak (see comparative example described later).
  • a conductive film is formed on the light metal by electroplating through a nickel-based undercoat
  • a special process such as an alternating current electrolytic process described in Patent Document 1 or a cathode activation process described in Patent Document 3 is used. If these operations are performed in parallel, improvement in adhesion can be expected.
  • a known nickel-based plating bath including a known nickel-phosphorous plating bath
  • the nickel-based plating bath described in Patent Documents 1 to 3 was used without undergoing such special operations. Even when electroplating is performed, the resulting nickel-based undercoat has poor adhesion (see Comparative Examples described below).
  • the present invention aims to strengthen the adhesion of conductive films such as silver, copper, and tin against a specific light metal selected from aluminum, magnesium, and titanium that easily form a non-conductive state. To do.
  • the inventors of the present invention When forming a conductive film on a specific light metal selected from aluminum, magnesium, and titanium that easily forms a non-conductive state, the inventors of the present invention have a nickel base between the light metal and the conductive film.
  • a nickel-phosphorus film is selected as the nickel-based undercoat, and the base coat is formed with a specific electric nickel-phosphorous plating bath to which a predetermined complexing agent, surfactant, etc. are added in combination. Then, it was found that the base film can be satisfactorily adhered onto a specific light metal selected from aluminum, magnesium, and titanium, and was previously proposed in Japanese Patent Application No. 2015-247207 (hereinafter referred to as the prior invention).
  • the present inventors formed a nickel-phosphorous undercoat on a specific light metal and then heat-treated the undercoat or formed a conductive film in the next step. If the base film and the conductive film are heat-treated later, the adhesion of the base film to the light metal can be further strengthened, so that the conductive film can be formed more firmly on the light metal, and the adhesion of the base film It was found that the temperature condition including a low temperature range of 30 ° C. or higher is sufficient for strengthening, and the present invention was completed.
  • the present invention 1 (S1) forming a base film made of a nickel-phosphorus film on a non-conductive formable light metal selected from aluminum, magnesium and titanium using an electric nickel-phosphorous plating bath; (S2) In a conductive film forming method comprising a step of forming a conductive film on a base film, Between the step (S1) and the step (S2), a step (S12) of heat-treating the base film at 30 ° C. or higher is interposed, or After the step (S2), a step (S3) of heat-treating the base film and the conductive film at 30 ° C.
  • the electric nickel-phosphorous plating bath is (a) a soluble nickel salt; (b) a compound containing phosphorus; (c) a complexing agent selected from aminocarboxylic acids, oxycarboxylic acids, carbohydrates, amino alcohols, polycarboxylic acids, and polyamines; (d) a surfactant selected from nonionic surfactants and amphoteric surfactants; (e) a buffering agent; (f) A method of forming a heat-treatable conductive film on a non-conductive-formable light metal, characterized by containing a brightener.
  • Present invention 2 is the present invention 1, wherein
  • the compound (b) containing phosphorus in the electric nickel-phosphorous plating bath is phosphorous acid, hypophosphorous acid, pyrophosphoric acid, orthophosphoric acid, hydroxyethylenediamine diphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) ) And at least one selected from the group consisting of these salts.
  • Present invention 3 is the present invention 1 or 2, wherein
  • the complexing agent (c) of the electric nickel-phosphorous plating bath is at least one selected from the group consisting of oxycarboxylic acids, polycarboxylic acids, and aminocarboxylic acids, and the oxycarboxylic acids are citric acid, tartaric acid, apple An acid, glycolic acid, and gluconic acid, the polycarboxylic acid is succinic acid, and the aminocarboxylic acid is selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid.
  • This is a heat treatment type conductive film forming method on a conductive formable light metal.
  • Invention 4 provides the method according to any one of Inventions 1 to 3, wherein The non-conductive formation, wherein the buffer (e) of the electro nickel-phosphorous plating bath is at least one selected from the group consisting of boric acid, sodium carbonate, sodium hydrogen carbonate, ascorbic acid, and salts thereof This is a heat treatment type conductive film forming method on a porous light metal.
  • the present invention 5 provides the method according to any one of the present inventions 1 to 4,
  • the brightener (f) for the electro-nickel-phosphorous plating bath is saccharin and its salt, benzenesulfonic acid and its salt, toluenesulfonic acid and its salt, naphthalenesulfonic acid and its salt, allylsulfonic acid and its salt, butynediol, ethylene
  • Non-passive formability characterized by being at least one compound selected from the group consisting of cyanohydrin, coumarin, propargyl alcohol, bis (3-sulfopropyl) disulfide, mercaptopropanesulfonic acid, and thiomalic acid
  • This is a heat treatment type conductive film forming method on a light metal.
  • the present invention 6 provides the method according to any one of the present inventions 1 to 5, A method for forming a heat-treatable conductive film on a non-conductive light-forming metal, characterized in that the pH of the electric nickel-phosphorous plating bath is 3.0 to 8.0.
  • Present invention 7 is any one of the present invention 1 to 6, wherein A method for forming a heat-treatable conductive film on a non-conductive-formable light metal, wherein the film thickness of the base film is 0.01 ⁇ m to 10.0 ⁇ m.
  • the present invention 8 provides the method according to any one of the present inventions 1 to 7,
  • the conductive film is formed by electroplating, electroless plating, sputtering, or vapor deposition,
  • the conductive film is a film made of a metal selected from copper, tin, silver, gold, nickel, bismuth, palladium, platinum, aluminum, magnesium, cobalt, zinc, and chromium, or an alloy of these metals. This is a heat treatment type conductive film forming method on a non-conductive-formable light metal.
  • a conductive film such as copper, tin, silver or the like is formed on a non-conductive film-type light metal selected from aluminum, magnesium, and titanium, a predetermined complexing agent, a surfactant, Using an electric nickel-phosphorous plating bath containing a buffering agent or the like to form a nickel-phosphorus coating on the light metal, and then forming a conductive coating, the base coating can be satisfactorily adhered onto the light metal.
  • a conductive film can be formed on the light metal with good adhesion.
  • the present invention is an improvement of this prior invention, and based on the processing steps of the prior application, a base film formed on a light metal, or a base film and a conductive film, is formed at a low temperature of 30 ° C. or higher.
  • a step of heat treatment under a temperature condition including the region, the adhesion of the base film on the light metal can be further strengthened, and the conductive film can be formed on the light metal with better adhesion.
  • the heat treatment for example, the adhesion of the base film on the light metal can be sufficiently strengthened by a simple heat treatment in a low temperature range such as hot water roasting at 30 ° C. to 100 ° C.
  • heat treatment is performed in a low temperature range, the energy to be dropped can be reduced and the productivity can be improved.
  • Patent Document 6 discloses that the adhesion of the plating layer to the aluminum alloy material is enhanced by covering the base material made of an aluminum alloy with an electric nickel plating layer and then performing heat treatment.
  • Patent Document 6 relates to a developing roller for a copying machine or the like, and a nickel plating layer with a low phosphorus content is used for the plating layer covering the aluminum alloy material because it is necessary to reduce the electrical resistance ([0019]. ]reference).
  • the plating layer covering the aluminum alloy material of Patent Document 6 is a nickel plating layer, which is different from the present invention in which a nickel-phosphorus film is used as a base film, and in Claim 4 of Patent Document 6,
  • the adhesion of the nickel layer to the aluminum alloy material can be improved by heat treatment, this requires improvement by heat treatment to ensure the adhesion sufficient to ensure reliability. It is unclear whether this means that the practical adhesion can be ensured without heat treatment, but the reliability of adhesion can be further enhanced by heating.
  • the specific composition of the electric nickel plating bath for forming the nickel layer is unknown.
  • the present invention provides a conductive film such as silver, copper, or tin on a specific light metal that easily forms a non-conductive state selected from aluminum, magnesium, and titanium via a base film made of a nickel-phosphorus film.
  • the base film and the conductive film are heat-treated at 30 ° C. or higher.
  • the above aluminum includes pure aluminum and an aluminum alloy
  • the above magnesium includes pure magnesium and a magnesium alloy
  • the above titanium includes pure titanium and a titanium alloy.
  • the present invention comprises the following undercoat film forming step (S1), conductive film forming step (S2), and a step of heat treatment between step (S1) and step (S2) or after step (S2).
  • S1 A step of forming a base film composed of a nickel-phosphorous film on a non-conductive formable light metal selected from aluminum, magnesium and titanium using an electric nickel-phosphorous plating bath (S2) on the base film
  • the electric nickel-phosphorous plating bath used in the step (S1) is: (A) a soluble nickel salt; (B) a compound containing phosphorus; (C) a complexing agent selected from aminocarboxylic acids, oxycarboxylic acids, carbohydrates, aminoalcohols, polycarboxylic acids, and polyamines; (D) a surfactant selected from nonionic surfactants and amphoteric surfactants; (E) a buffer; (F) A brightener is an essential component.
  • the soluble nickel salt (a) contained in the electro-nickel-phosphorous plating bath only needs to be able to supply nickel ions into the plating bath.
  • Nickel sulfate, nickel chloride, nickel ammonium sulfate, nickel oxide, nickel acetate, nickel carbonate Nickel oxalate, nickel sulfamate, nickel salt of organic sulfonic acid and the like, and nickel sulfate, nickel sulfamate, nickel oxide and the like are preferable.
  • the phosphorus-containing compound (b) contained in the electric nickel-phosphorous plating bath includes phosphorous acid, hypophosphorous acid, pyrophosphoric acid, orthophosphoric acid, hydroxyethylenediamine diphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediamine Examples include tetra (methylene phosphonic acid) and salts thereof.
  • the soluble nickel salt (a) can be used alone or in combination, and its content in the plating bath is 0.01 mol / L to 3.0 mol / L, preferably 0.05 mol / L to 2.0 mol / L. L, more preferably 0.1 mol / L to 1.5 mol / L.
  • the phosphorus-containing compound (b) can be used singly or in combination, and its content in the plating bath is 0.05 mol / L to 2.0 mol / L, preferably 0.1 mol / L to 1.0 mol. / L, more preferably 0.1 mol / L to 0.8 mol / L.
  • the complexing agent (c) contained in the electro-nickel-phosphorous plating bath is a compound that mainly forms a nickel complex in the plating bath, and makes the change in the cathode current density with respect to the change in the electrode potential gentle. It fulfills the function of facilitating film deposition.
  • the complexing agent (c) is selected from the group consisting of aminocarboxylic acids, oxycarboxylic acids, saccharides, aminoalcohols, polycarboxylic acids, and polyamines.
  • aminocarboxylic acids examples include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, nitrilotriacetic acid (NTA).
  • EDTA ethylenediaminetetraacetic acid
  • HEDTA hydroxyethylethylenediaminetriacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • TTHA triethylenetetraminehexaacetic acid
  • NTA nitrilotriacetic acid
  • Iminodiacetic acid IDA
  • iminodipropionic acid IDP
  • metaphenylenediaminetetraacetic acid 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid, and salts thereof
  • NTA, EDTA, and DTPA are preferable.
  • the oxycarboxylic acids include citric acid, tartaric acid, malic acid, glycolic acid, gluconic acid, lactic acid, glucoheptonic acid, and salts thereof, citric acid, tartaric acid, malic acid, glycolic acid, gluconic acid, and These salts are preferred.
  • sugars examples include glucose (glucose), fructose (fructose), lactose (lactose), maltose (maltose), isomaltulose (palatinose), xylose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol , Reduced isomaltulose, gluconolactone and the like, and sugar alcohols such as sorbitol, xylitol, mannitol, maltitol are preferred.
  • Examples of the amino alcohols include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine, with triethanolamine and tripropanolamine being preferred.
  • Examples of the polycarboxylic acids include succinic acid, oxalic acid, glutaric acid, adipic acid, malonic acid, and salts thereof, and succinic acid is preferable.
  • Examples of the polyamines include methylene diamine, ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene triamine, tetraethylene pentamine, pentaethylene hexamine, and hexaethylene heptamine, and ethylene diamine is preferred.
  • the complexing agent (c) examples include oxycarboxylic acids such as citric acid, tartaric acid, malic acid, glycolic acid, and gluconic acid, polycarboxylic acids such as succinic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and Amino carboxylic acids such as these salts, and saccharides such as sorbitol, mannitol, maltitol are preferred.
  • the complexing agent (c) can be used alone or in combination, and its content in the plating bath is 0.001 mol / L to 2 mol / L, preferably 0.05 mol / L to 0.8 mol / L. L, more preferably 0.1 mol / L to 0.5 mol / L.
  • the surfactant (d) contained in the electric nickel-phosphorus plating bath is selected from nonionic surfactants and amphoteric surfactants, and a non-conductive formable light metal selected from aluminum, magnesium, and titanium and a base Improves adhesion to the film.
  • the nonionic surfactants are generally C1-C20 alkanols, phenols, naphthols, bisphenols, (poly) C1-C25 alkylphenols, (poly) arylalkylphenols, C1-C25 alkylnaphthols, C1-C25 alkoxylations.
  • ethylene oxide (EO) and / or propylene oxide (PO) is added to phosphoric acid (salt), sorbitan ester, polyalkylene glycol, polyoxyalkylene phenyl ether, C1-C22 aliphatic amine, C1-C22 aliphatic amide, etc. Examples include those subjected to molar addition condensation.
  • polyoxyethylene cumyl phenyl ether polyoxyethylene dodecyl phenyl ether, dibutyl- ⁇ -naphthol polyethoxylate, polyoxyethylene styrenated phenyl ether, ethylenediamine / tetrapolyoxyethylene / polyoxypropylene, polyethylene glycol, lauryl alcohol Polyethoxylates are preferred.
  • amphoteric surfactant include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid betaine.
  • lauryldimethylaminoacetic acid betaine for example, lauryldimethylaminoacetic acid betaine, stearic acid amidopropyl betaine, lauric acid amidopropyldimethylamine oxide, and the like are suitable.
  • sulfated adducts or sulfonated adducts of condensation products of ethylene oxide (EO) and / or propylene oxide (PO) with alkylamines or diamines can also be used.
  • the surfactant (d) can be used alone or in combination, and its content in the plating bath is 0.1 g / L to 50 g / L, preferably 1 g / L to 40 g / L, more preferably 5 g / L. ⁇ 35 g / L.
  • the addition of a nonionic surfactant and / or an amphoteric surfactant is an essential requirement from the viewpoint of improving adhesion.
  • a surfactant other than the specific species that is, a cationic surfactant and / or an anionic surfactant in combination.
  • a cationic surfactant and / or an anionic surfactant is added alone without adding the predetermined surfactant of the present invention to the plating bath, the stability of the plating bath and the adhesion of the base film The point that does not contribute to is as shown in a test example (see Comparative Example 7) described later.
  • the buffering agent (e) contained in the electric nickel-phosphorus plating bath improves the adhesion of the base film composed of a nickel-phosphorus film to a non-conductive forming light metal selected from aluminum, magnesium, and titanium, and Also acts as a stabilizer for the plating bath.
  • the buffer (e) include boric acid, sodium carbonate, sodium bicarbonate, ascorbic acid, and salts thereof, and boric acid and sodium carbonate are preferable.
  • the buffer (e) can be used alone or in combination, and its content in the plating bath is 0.05 mol / L to 1.5 mol / L, preferably 0.05 mol / L to 1.0 mol. / L, more preferably 0.1 mol / L to 0.6 mol / L.
  • the brightener (f) contained in the electric nickel-phosphorous plating bath improves the adhesion of the base film made of a nickel-phosphorous film to a non-conductive forming light metal selected from aluminum, magnesium and titanium.
  • the brightener (f) include saccharin and salts thereof, benzenesulfonic acid and salts thereof, toluenesulfonic acid (specifically, p-toluenesulfonic acid and the like) and salts thereof, naphthalenesulfonic acid and salts thereof, and allylsulfone.
  • Acids and salts thereof include butynediol (specifically, 2-butyne-1,4-diol, etc.), ethylene cyanohydrin, coumarin, propargyl alcohol, bis (3-sulfopropyl) disulfide, mercaptopropanesulfonic acid, And compounds such as thiomalic acid.
  • the brightener (f) it is effective to use each compound alone, but in particular, benzenesulfonic acid or a salt thereof and saccharin, naphthalenesulfonic acid or a salt thereof and saccharin, butynediol and benzenesulfonic acid or a salt thereof.
  • Salt butynediol and naphthalenesulfonic acid or salt thereof, allylsulfonic acid or salt and saccharin, thiomalic acid and saccharin, bis (3-sulfopropyl) disulfide and saccharin, allylsulfonic acid or salt thereof and propargyl alcohol, benzenesulfone It is preferable to use two or more compounds in combination, such as acid or a salt thereof and propargyl alcohol, naphthalenesulfonic acid or a salt thereof and propargyl alcohol.
  • the brightener (f) can be used alone or in combination, and its content in the plating bath is 0.001 mol / L to 0.15 mol / L, preferably 0.005 mol / L to 0. 0.07 mol / L, more preferably 0.01 mol / L to 0.05 mol / L.
  • an electric nickel-phosphorous plating bath is intended to form a base film comprising a nickel-phosphorous film on a non-conductive non-forming light metal selected from aluminum, magnesium and titanium.
  • the pH of the bath is suitably from 3.0 to 8.0, preferably from 4.0 to 6.0.
  • the primer film forming step (S1), the cathode current density during the electroplating 0.01A / dm 2 ⁇ 5.0A / dm 2, preferably at 0.05A / dm 2 ⁇ 2.0A / dm 2 is there.
  • the nickel-phosphorus film as the undercoat film is not required to be formed thick because it only needs to provide conductivity and adhesion sufficient to form a conductive film on the upper layer. Accordingly, the film thickness is 0.01 ⁇ m to 10.0 ⁇ m, preferably 0.01 ⁇ m to 8.0 ⁇ m, more preferably 0.01 ⁇ m to 5.0 ⁇ m.
  • the step (S1) of forming a base coating composed of a nickel-phosphorus coating on a non-conductive formable light metal selected from aluminum, magnesium and titanium has been described in detail.
  • the step (S1) The step (S2) of forming a conductive film as an upper film on the nickel-phosphorus film formed in (1) will be described.
  • the conductive film is not particularly limited as long as it is a known film having conductivity, for example, copper, tin, silver, gold, nickel, bismuth, palladium, platinum, aluminum, magnesium, cobalt, zinc, and Examples thereof include a film made of a metal selected from chromium or an alloy of these metals.
  • Silver, copper, nickel, tin, palladium, gold, and bismuth are suitable as the metal constituting the conductive film.
  • the metal alloys include nickel-tungsten alloys, nickel-molybdenum alloys, nickel-tin alloys, tin-silver alloys, tin-bismuth alloys, tin-copper alloys, tin-zinc alloys, and gold-tin alloys. Is preferred.
  • the conductive film can be formed by electroplating, electroless plating, sputtering or vapor deposition. Among these, the plating method is preferable from the viewpoint of productivity, but does not exclude sputtering or vapor deposition.
  • the method of the present invention is characterized in that a conductive film is formed on a non-conductive light-forming metal via a base film, and the conductive film may be formed as a single layer, or may be formed into two layers or three layers. It is also possible to form a multi-layer.
  • a multi-layered conductive film is made of a metal selected from nickel, copper, cobalt, bismuth, zinc, chromium, iron, or an alloy of these metals as the lower layer (that is, the side facing the base film).
  • the uppermost layer of the multi-layered conductive film is formed of tin, nickel, cobalt, chromium, silver, palladium, or an alloy thereof, a beautiful silver appearance can be imparted to the surface of the uppermost layer.
  • the present invention is characterized in that a heat treatment process is added as an essential constituent element to the base film forming process (S1) and the conductive film forming process (S2). Therefore, this heat treatment step will be described in detail.
  • the first method of heat treatment is to interpose the heat treatment step (S12) between the base film formation step (S1) and the conductive film formation step (S2). It consists of a process.
  • S1 A step of forming a base film made of a nickel-phosphorous film on a non-conductive formable light metal such as aluminum using an electric nickel-phosphorous plating bath (S12) a step of heat-treating the base film at 30 ° C.
  • the base film is heat-treated at 30 ° C. or higher to further improve the adhesion of the base film to the non-conductive formable light metal. Therefore, the conductive film can be formed more firmly on the non-conductive light metal.
  • the heat treatment temperature is suitably 30 ° C to 300 ° C, preferably 30 ° C to 250 ° C, more preferably 30 ° C to 200 ° C, still more preferably 30 ° C to 150 ° C, and particularly preferably 30 ° C to 100 ° C. It is. Even if the heat treatment temperature is higher than 300 ° C., the effect of strengthening the adhesion is not changed so much.
  • the upper limit of the heat treatment temperature is preferably about 200 ° C.
  • the practical adhesion of the base film to the non-conductive formable light metal is The lower limit of the heat treatment temperature was set to 30 ° C., since it can be guaranteed and further improvement in adhesion can be expected even with heating at about 30 ° C. with respect to this practical level.
  • the second method of heat treatment is a method in which a heat treatment step (S3) is added after the conductive film formation step (S2), and this subsequent heat treatment method includes the following three steps.
  • S1 A step of forming a base film composed of a nickel-phosphorus film on a non-conductive light-forming metal such as aluminum using an electric nickel-phosphorous plating bath (S2)
  • S3 A conductive film is formed on the base film Step (S3) Step of heat-treating the base film and the conductive film at 30 ° C. or higher
  • the temperature condition of the heat treatment in the second method may be the same as in the first method.
  • an intermediate heat processing system and a post-stage heat processing system are common, various aspects, such as oven heating, hot air heating with a dryer, immersion in warm water or an oil bath, can be selected.
  • various aspects such as oven heating, hot air heating with a dryer, immersion in warm water or an oil bath, can be selected.
  • hot water treatment at 30 ° C to 100 ° C boiling water bath immersed in hot water
  • the heat treatment is performed in a low temperature range with hot water bath, so heat energy can be reduced and the processing can be simplified. Can be improved.
  • an electro-nickel-phosphorus plating bath for forming a base film (nickel-phosphorus film) on a non-conductive-forming light metal such as aluminum a plating bath for forming a conductive film, and a heat treatment method on the light metal.
  • An example of a method for forming a conductive film through the base film will be described, and an evaluation test example of the adhesion of the nickel-phosphorus film to the light metal will be sequentially described.
  • the present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
  • Example of a method for forming a conductive film on a non-conductive formable light metal by a heat treatment method In Examples 1 to 13 below, the base film and the conductive film are as follows. Examples 1 to 7: Nickel-phosphorus film (undercoat film) / tin film (conductive film) Example 8: Nickel-phosphorus film (undercoat film) / copper film (conductive film) Example 9: Nickel-phosphorus film (undercoat film) / nickel film (conductive film) Examples 10 and 13: Nickel-phosphorus film (undercoat film) / silver film (conductive film) Example 11: Nickel-phosphorus film (undercoat film) / palladium film (conductive film) Example 12: Nickel-phosphorus coating (undercoat) / tin-bismuth alloy coating (conductive coating) In Example 13, the conductive film (silver film) was formed by electroless plating, and in other examples, it was formed by electroplating.
  • Examples 1 to 7 are examples in which the composition of the nickel-phosphorus plating bath in step (S1) was changed.
  • Examples 1 to 13 are examples of an intermediate heat treatment method in which a heat treatment step (S12) is interposed between the base film formation step (S1) and the conductive film formation step (S2).
  • 17 is an example of a post-stage heat treatment method in which a heat treatment step (S3) is added after the above step (S2).
  • Examples 18 to 23 described below are the undercoat film formation step (S1) and the conductive film formation step (S2). ) Is an example of an intermediate heat treatment method in which a heat treatment step (S12) is interposed.
  • Example 14 is based on Example 1
  • Example 15 is based on Example 3
  • Example 16 is based on Example 8
  • Example 17 is This is based on Example 9.
  • Examples 1 to 17 are examples of hot water roasting at 70 ° C. for 5 minutes
  • Examples 18 to 20 are examples of hot water roasting by changing the conditions
  • Examples 21 is an example of heating with hot air
  • Examples 22 to 23 are examples of heating with oven.
  • the reference example is an example of the invention of the prior application described above, and is an example in which, based on Example 1, the process (S1) is directly transferred to the process (S2) after the process (S1).
  • Comparative Examples 1 to 9 below are based on Example 1 with the following modifications.
  • Comparative Example 1 Blank example in which a conductive film was directly formed by electroplating without forming a base film on a light metal (example without heat treatment)
  • Comparative Examples 2 to 3 An example in which a conductive film is formed on a light metal via a base film that is a nickel film instead of a nickel-phosphorus film
  • Comparative Example 2 an example in which heat treatment was performed
  • Comparative Example 3 an example in which heat treatment was not performed
  • Comparative Examples 4 to 9 The nickel-phosphorous plating bath used in the base film forming step (S1) in the method of the present invention does not contain some essential components, or some essential components become other components.
  • Comparative Example 4 Examples in which the complexing agent (c) is not contained in the nickel-phosphorous plating bath Comparative Examples 5 to 6: Examples in which the surfactant (d) is not contained in the nickel-phosphorous plating bath Comparative Example 5: Example of heat treatment Comparative Example 6: Example without heat treatment Comparative Example 7: Example of heat treatment using a cationic surfactant instead of the surfactant (d) used in the present invention in a nickel-phosphorus plating bath Comparative Example 8 ⁇ 9: Glossy nickel-phosphorus plating bath Example in which agent (f) is not included Comparative Example 8: Example in which heat treatment was performed Comparative Example 9: Example in which heat treatment was not performed
  • Example 1 (S1) Undercoat forming step As shown in the following (i) to (iv), three types of 5 cm ⁇ 5 cm square aluminum alloy plates and one type of 5 cm ⁇ 5 cm square magnesium alloy plates were prepared. Each sample of conductive state-forming light metal was used (the same applies to Examples 2 to 22 and Comparative Examples 1 to 9 below). In particular, the three types of aluminum alloys were selected because of the variety of types of the alloys. Therefore, even if the type of aluminum alloy changes, the versatility of whether or not the undercoat of the present invention can be applied with good adhesion is provided. This is for verification.
  • Sample 1 Aluminum alloy / Al-Cu system (A2024P; JIS standard)
  • Sample 2 Aluminum alloy / Al-Mg system (A5052P; JIS standard)
  • Sample 3 Aluminum alloy / Al-Mg-Si system (A6061P; JIS standard)
  • Sample 4 Magnesium alloy / Mg—Al—Zn system (AZ31; JIS standard)
  • Example 2 Undercoat Forming Step Based on Example 1, the soluble nickel salt (a) in the electric nickel-phosphorous plating bath was changed. The compound (b) containing phosphorus and the complexing agent (c) were also changed slightly.
  • Example 3 Undercoat Formation Step Based on Example 1, the compound (b) containing phosphorus in the electric nickel-phosphorous plating bath was changed.
  • A Composition of nickel-phosphorous plating bath and electroplating conditions An electric nickel-phosphorous plating bath was constructed with the following composition.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Sodium hypophosphite 0.4 mol / L Citric acid 0.3 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 5.0 [Electroplating conditions] Bath temperature: 40 ° C Current density: 0.1 A / dm 2 Plating time: 2 minutes [plating film] Film thickness: 0.01 ⁇ m Phosphorus content: 4.5% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Example 4 Undercoat Forming Step Based on Example 1, the complexing agent (c) for the electric nickel-phosphorous plating bath was changed.
  • A Composition of nickel-phosphorous plating bath and electroplating conditions An electric nickel-phosphorous plating bath was constructed with the following composition.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Phosphorous acid 0.4 mol / L Sodium gluconate 0.3mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 24% aqueous sodium hydroxide) 5.0 [Electroplating conditions] Bath temperature: 40 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 5.0% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Example 5 Undercoat Formation Step Based on Example 1, the nonionic surfactant (d) in the electric nickel-phosphorus plating bath was changed.
  • A Composition of nickel-phosphorous plating bath and electroplating conditions An electric nickel-phosphorous plating bath was constructed with the following composition.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Sodium hydrogen phosphite 2.5 hydrate 0.4 mol / L Citric acid 0.3 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Polyoxyethylene octyl phenyl ether (EO 10 mol) 10g / L pH (adjusted with 24% aqueous sodium hydroxide) 4.5 [Electroplating conditions] Bath temperature: 40 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 3.0% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Example 6 Undercoat Forming Step Based on Example 1, the buffer (e) for the electric nickel-phosphorous plating bath was changed.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Sodium carbonate 0.2mol / L Phosphorous acid 0.4 mol / L Trisodium citrate dihydrate 0.3 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 5.0% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Example 7 Base film forming step Based on Example 1, the brightening agent (f) of the electric nickel-phosphorus plating bath was changed.
  • A Composition of nickel-phosphorous plating bath and electroplating conditions An electric nickel-phosphorous plating bath was constructed with the following composition.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Sodium carbonate 0.2mol / L Phosphorous acid 0.4 mol / L Trisodium citrate dihydrate 0.3 mol / L 2-butyne-1,4-diol 0.02 mol / L Benzenesulfonic acid 0.01 mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 5.0% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions:
  • Example 8 (S1) Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a copper film. (B) Composition of copper plating bath and electroplating conditions An electrolytic copper plating bath was constructed with the following composition.
  • composition Copper sulfate pentahydrate (as Cu 2+ ) 0.8 mol / L Sulfuric acid 1.0 mol / L Hydrochloric acid 0.1mmol / L Bis (3-sulfopropyl) disulfide 1.0mg / L Polyethylene glycol (molecular weight 4000) 1.0g / L Polyethyleneimine 3.0mg / L [Electroplating conditions] Bath temperature: 25 ° C Current density: 1 A / dm 2 Plating time: 5 minutes [plating film] Film thickness: 10 ⁇ m
  • Example 9 (S1) Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a nickel film. (B) Composition of nickel plating bath and electroplating conditions An electronicking bath was constructed with the following composition.
  • Nickel sulfate hexahydrate (as Ni 2+ ) 0.15 mol / L
  • Nickel chloride (as Ni 2+ ) 0.5 mol / L Boric acid 0.7mol / L pH (adjusted with 28% ammonia water)
  • Bath temperature 60 ° C
  • Current density 1 A / dm 2
  • Plating time 5 minutes
  • Film thickness 10 ⁇ m
  • Example 10 (S1) Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a silver film. (B) Composition of silver plating bath and electroplating conditions An electrosilver plating bath was constructed with the following composition.
  • Example 11 Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a palladium film.
  • B Composition of palladium plating bath and electroplating conditions An electropalladium plating bath was constructed with the following composition.
  • Example 12 (S1) Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a tin-bismuth alloy film.
  • B Composition of tin-bismuth alloy plating bath and electroplating conditions An electrotin-bismuth alloy plating bath was constructed with the following composition.
  • Example 13 (S1) Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S12) Heat treatment process Heat treatment conditions: Same as in Example 1 (S2) Conductive film formation process Based on Example 1 The conductive film was changed to a silver film.
  • B Composition of silver plating bath and electroless plating conditions An electroless silver plating bath was constructed with the following composition. [composition] Silver nitrate (as Ag + ) 0.01 mol / L Succinimide 0.05 mol / L Imidazole 0.05 mol / L [Electroless plating conditions] Bath temperature: 50 ° C Plating time: 60 minutes [plating film] Film thickness: 1.0 ⁇ m
  • Example 14 Based on Example 1, instead of performing heat treatment between Step (S1) and Step (S2), heat treatment was performed after Step (S2) (an example of post-stage heat treatment.
  • Step (S2) an example of post-stage heat treatment.
  • Examples 15 to 17 are the same) ).
  • S1 Undercoat film formation process Electroplating conditions: Same as in Example 1 Undercoat film: Nickel-phosphorus film (S2) Conductive film formation process Electroplating conditions: Same as in Example 1 Conductive film: Tin film (S3) Heat treatment Process heat treatment conditions: same as step (S12) of Example 1
  • Example 15 Based on Example 3, it heat-processed after the said process (S2) instead of heat-processing between a process (S1) and a process (S2).
  • S1 Undercoat film formation process
  • Electroplating conditions Same as in Example 3
  • Undercoat film Nickel-phosphorus film
  • Conductive film formation process Electroplating conditions: Same as in Example 3
  • Conductive film Tin film
  • Example 16 Based on Example 8, instead of performing heat treatment between step (S1) and step (S2), heat treatment was performed after the step (S2). (S1) Undercoat film formation process Electroplating conditions: Same as in Example 8 Undercoat film: Nickel-phosphorus film (S2) Conductive film formation process Electroplating conditions: Same as in Example 8 Conductive film: Copper film (S3) Heat treatment Process heat treatment conditions: same as step (S12) of Example 8
  • Example 17 Based on Example 9, heat treatment was performed after the step (S2) instead of heat treatment between the step (S1) and the step (S2).
  • S1 Undercoat film formation process Electroplating conditions: Same as in Example 9 Undercoat film: Nickel-phosphorous film (S2) Conductive film formation process Electroplating conditions: Same as in Example 9 Conductive film: Nickel film (S3) Heat treatment Process heat treatment conditions: same as step (S12) of Example 9
  • Example 18 Based on Example 1, the heat treatment conditions in the step (S12) were changed (hereinafter, Examples 19 to 23 are the same).
  • S1 Undercoat film forming step Electroplating conditions: Same undercoat as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorus film was formed was bathed under the following conditions. [Heat treatment conditions] Bath temperature: 35 ° C Bath time: 80 minutes (S2) Conductive film formation process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Example 19 Based on Example 1, the heat treatment conditions in the step (S12) were changed.
  • S1 Undercoat film forming step Electroplating conditions: Same undercoat as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorus film was formed was bathed under the following conditions. [Heat treatment conditions] Bath temperature: 50 ° C Bathing time: 30 minutes (S2) Conductive film forming process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Example 20 Based on Example 1, the heat treatment conditions in the step (S12) were changed.
  • S1 Undercoat film forming step Electroplating conditions: Same undercoat as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorus film was formed was bathed under the following conditions. [Heat treatment conditions] Hot water temperature: 90 ° C Bath time: 10 minutes (S2) Conductive film formation process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Example 21 Based on Example 1, the heat treatment conditions in the step (S12) were changed.
  • S1 Undercoat film forming step Electroplating conditions: Undercoat film as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorus film was formed was heated with a dryer under the following conditions. [Heat treatment conditions] Hot air heating temperature: 150 ° C Heating time: 5 minutes (S2) Conductive film forming process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Example 22 Based on Example 1, the heat treatment conditions in the step (S12) were changed.
  • S1 Undercoat film forming step Electroplating conditions: Same undercoat as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorous film was formed was oven-heated under the following conditions. [Heat treatment conditions] Oven heating temperature: 150 ° C Heating time: 10 minutes (S2) Conductive film formation process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Example 23 Based on Example 1, the heat treatment conditions in the step (S12) were changed.
  • S1 Undercoat film forming step Electroplating conditions: Same undercoat as in Example 1: Nickel-phosphorus film (S12) heat treatment step Next, each sample on which the nickel-phosphorous film was formed was oven-heated under the following conditions. [Heat treatment conditions] Oven heating temperature: 200 ° C Heating time: 5 minutes (S2) Conductive film forming process Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Trisodium citrate dihydrate 0.3 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 1.0 ⁇ m (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Phosphorous acid 0.4 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes Since the plating bath was decomposed, the formation of the undercoat could not be carried out, and the next heat treatment step (S12) was not achieved.
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Phosphorous acid 0.4 mol / L Trisodium citrate dihydrate 0.3 mol / L Saccharin 0.02 mol / L Thiomalic acid 0.01mol / L Lauryltrimethylammonium chloride 20g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 5.0% (S2) Conductive film formation step Electroplating conditions: Same as Example 1 Conductive film: Tin film
  • Nickel sulfamate (as Ni 2+ ) 0.45 mol / L Nickel chloride (as Ni 2+ ) 0.03 mol / L Boric acid 0.2mol / L Phosphorous acid 0.4 mol / L Trisodium citrate dihydrate 0.3 mol / L Ethylenediaminetetrapolyoxyethylene (EO 40 mol) polyoxypropylene (PO 50 mol) 10 g / L pH (adjusted with 28% ammonia water) 4.5 [Electroplating conditions] Bath temperature: 35 ° C Current density: 0.5 A / dm 2 Plating time: 10 minutes [plating film] Film thickness: 0.2 ⁇ m Phosphorus content: 5.0% (S12) Heat treatment process heat treatment conditions: the same as in Example 1 (S2) Conductive film formation process Electroplating conditions: the same as in Example 1 Conductive film: Tin film
  • Example of evaluation test of adhesion of base film to non-forming light metal When the adhesion of the undercoat to the non-conductive light metal increases, the adhesion of the upper conductive film to the light metal is improved. Therefore, the evaluation test of the adhesive strength was evaluated based on the superiority or inferiority of the adhesive strength of the base film (formed in close contact with the conductive film) against the light metal. In addition, although the test is evaluated by the adhesion strength of the ground film, except for some comparative examples, in each example, reference example, and comparative example, the point that both the conductive film formation process is performed As described above.
  • Table 3 below shows the results of an evaluation test of the adhesion of the base film to the non-conductive-forming light metal.
  • magnesium alloys are not as diverse as aluminum alloys, only the examples 1 and 2 were evaluated for the magnesium alloy plate of Sample 4. Based on the test results of Examples 1 and 2, evaluations of Examples 3 to 23 other than these were estimated (indicated as “-” in Table 3 below). Further, in Comparative Examples 1 and 4, since the undercoat could not be formed on the light metal, the undercoat peel test itself was not performed (indicated as “-” in Table 3 below).
  • the said base film shows favorable adhesiveness also to the sample 4, it turns out that a conductive film can be formed with sufficient adhesiveness also through a base film also with respect to a magnesium alloy.
  • the adhesion of the undercoat to the light metal was further improved as compared to the above reference example.
  • the undercoat was formed from the light metal plates (samples 1 to 3) It can be seen that the three types of aluminum alloy plates are more firmly attached.
  • the adhesion strength in Examples 1 to 23 was the same as that of the reference example, and the adhesion strength was good.
  • Comparative Example 3 the base film formed by electroplating on the light metal was changed from the nickel-phosphorus film to the nickel film, and the base film was not heat-treated.
  • the light metal plate (aluminum alloy plate)
  • the adhesion strength of the nickel film to the nickel-phosphorus film is greatly inferior to that of the nickel-phosphorus film ( ⁇ evaluation). Therefore, it was not possible to form a conductive film (tin film) with good adhesion on the non-conductive light-forming metal.
  • Comparative Example 2 in which the base film, which is a nickel film, was heat-treated, the adhesion was improved as compared with Comparative Example 3 without heat treatment ( ⁇ evaluation), but was not as good as the reference example ( ⁇ evaluation).
  • Comparative Example 4 an undercoat was formed on a light metal with a nickel-phosphorous plating bath not containing the predetermined complexing agent (c) used in the present invention, but precipitation occurred because the plating bath was unstable. It occurred and an electrodeposition film could not be formed. Therefore, when this Comparative Example 4 is compared with Examples 1 to 23, in order to form a strong nickel-phosphorus undercoat on a light metal, a predetermined complexing agent (c) is used instead of a conventionally known nickel-phosphorous plating bath. The importance of selecting a nickel-phosphorous plating bath for use in the present invention containing) was revealed.
  • Comparative Example 6 a base film was formed on a light metal with a nickel-phosphorous plating bath not containing the predetermined surfactant (d) used in the present invention, and the base film was not heat-treated.
  • the adhesion of the base film to the alloy plate is greatly inferior (x evaluation). Therefore, in Comparative Example 6, a conductive film (tin film) could not be formed with good adhesion on the non-conductive formable light metal.
  • Comparative Example 5 in which the same undercoat as that in Comparative Example 6 was heat-treated, the adhesion was improved as compared with Comparative Example 6 without heat treatment ( ⁇ evaluation), but did not reach the reference example ( ⁇ evaluation).
  • Comparative Example 7 an undercoat was formed on a light metal with a nickel-phosphorus plating bath containing a cationic surfactant instead of the surfactant (d) used in the present invention (no heat treatment).
  • the adhesion of the base film to the aluminum alloy plate is greatly inferior (x evaluation). Therefore, in Comparative Example 7, a conductive film (tin film) could not be formed with good adhesion on the nonconductive state-forming light metal. Therefore, when this Comparative Example 7 is compared with Examples 1 to 23, in order to realize more practical and strong adhesion, the nickel-phosphorous plating bath was specialized in the present invention, not a cationic surfactant. It can be judged that it is important to contain the surfactant (d) and to heat-treat the undercoat.
  • Comparative Example 9 a base film was formed on a light metal in a nickel-phosphorous plating bath not containing the predetermined brightener (f) used in the present invention, and the base film was not heat-treated.
  • the adhesion of the base film to the alloy plate is greatly inferior (x evaluation). Therefore, in Comparative Example 9, a conductive film (tin film) could not be formed with good adhesion on the nonconductive state-forming light metal.
  • Comparative Example 8 in which the same undercoat as in Comparative Example 9 was heat-treated, the adhesion was improved as compared with Comparative Example 9 without heat treatment ( ⁇ evaluation), but did not reach the reference example ( ⁇ evaluation).
  • Examples 1 to 23 will be described in detail focusing on heat treatment.
  • Examples 1 to 7 are examples in which the conductive film is a tin film
  • Example 8 is an example in which the conductive film is a copper film
  • Example 9 is an example in which the conductive film is a nickel film
  • Examples 10 and 13 are conductive.
  • Example 11 is an example in which the conductive film is a silver film
  • Example 11 is an example in which the conductive film is a palladium film
  • Example 12 is an example in which the conductive film is a tin-bismuth film.
  • the composition of the nickel-phosphorus plating bath used in the step (S1) that is, the complexing agent (c), the surfactant (d), the soluble nickel salt (a), the phosphorus-containing compound (b ), The type of the brightener (f) and the like are changed.
  • the adhesion of the base film is different from that of the reference example even if the composition of the plating bath is different. It can be seen that it can be greatly improved.
  • Examples 1 to 13 are intermediate heat treatment methods in which the heat treatment step (S12) is performed between the base film formation step (S1) and the conductive film formation step (S2).
  • Examples 14 to 17 are post-stage heat treatment methods in which the heat treatment step (S3) is performed after the conductive film formation step (S2). Either method can greatly enhance the adhesion of the underlying film, and the conductive film can be formed more firmly on the light metal compared to the standard example, so that the adhesion can be strengthened regardless of the timing conditions of the heat treatment. Can be judged. Focusing on the additional conditions of the heat treatment, Examples 1 to 17 were examples of water bathing at 70 ° C. for 20 minutes, Example 18 was water bathing at 35 ° C.
  • Example 19 was 50 ° C. for 30 minutes.
  • An example of hot water roasting Example 20 is an example of hot water roasting at 90 ° C. for 10 minutes.
  • the hot water bath which is a relatively simple heating means, and by heating in a low temperature range of 100 ° C. or lower, the adhesion of the base film can be greatly improved as compared with the reference example.
  • the adhesion could be enhanced by continuing the heat treatment over time even in a very low temperature range (35 ° C.). If a heat treatment in a relatively high temperature range such as dryer heating as in Example 21 or oven heating as in Examples 22 to 23 is selected instead of hot water bath, the heating time can naturally be shortened.
  • hot water bathing is selected as a heat treatment condition, the input of heat energy can be reduced and productivity can be improved.
  • the adhesion of the base film on the light metal can be further strengthened, and the conductive film can be formed on the light metal with better adhesion, thereby improving the productivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un procédé de formation d'un revêtement électroconducteur d'argent, de cuivre, d'étain ou similaire par l'intermédiaire d'un revêtement de base sur un métal léger formant un état passif choisi parmi l'aluminium, le magnésium et le titane, le revêtement de base étant un revêtement nickel-phosphore, le revêtement de base étant formé au moyen d'un bain galvanoplastique nickel-phosphore comprenant un sel de nickel soluble prédéfini, un composé comprenant du phosphore, un agent complexant, un tensioactif, un tampon, et un agent d'avivage, et le revêtement de base ou le revêtement de base et le revêtement électroconducteur sont traités thermiquement dans des conditions comprenant une plage de température d'au moins 30 °C, moyennant quoi l'adhérence du revêtement de base au métal léger formant un état passif est augmentée par rapport à un procédé ne comprenant pas de traitement thermique, et le revêtement électroconducteur peut être formé avec une adhérence plus forte sur le métal léger formant un état passif.
PCT/JP2017/035477 2016-10-25 2017-09-29 Procédé de type traitement thermique destiné à la formation d'un revêtement électroconducteur sur un métal léger formant un état passif WO2018079188A1 (fr)

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CN201780066043.1A CN109891004B (zh) 2016-10-25 2017-09-29 钝态形成性轻金属上的热处理式导电性被膜形成方法
KR1020217011088A KR102409545B1 (ko) 2016-10-25 2017-09-29 부동태 형성성 경금속 상의 열처리식 도전성 피막 형성 방법

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CN113737233A (zh) * 2021-06-23 2021-12-03 中国科学院深圳先进技术研究院 一种Fe-Ni-P合金电镀液、Fe-Ni-P合金镀层的电沉积方法及合金镀层

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