WO2009099067A1 - Structure plaquée - Google Patents

Structure plaquée Download PDF

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Publication number
WO2009099067A1
WO2009099067A1 PCT/JP2009/051798 JP2009051798W WO2009099067A1 WO 2009099067 A1 WO2009099067 A1 WO 2009099067A1 JP 2009051798 W JP2009051798 W JP 2009051798W WO 2009099067 A1 WO2009099067 A1 WO 2009099067A1
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WO
WIPO (PCT)
Prior art keywords
palladium
reducing agent
plating layer
palladium plating
layer
Prior art date
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PCT/JP2009/051798
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English (en)
Japanese (ja)
Inventor
Takashi Kubota
Original Assignee
Sekisui Chemical Co., Ltd.
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Filing date
Publication date
Application filed by Sekisui Chemical Co., Ltd. filed Critical Sekisui Chemical Co., Ltd.
Priority to JP2009505671A priority Critical patent/JP4351736B2/ja
Publication of WO2009099067A1 publication Critical patent/WO2009099067A1/fr

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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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands

Definitions

  • the present invention relates to a plated structure that achieves extremely high conductivity.
  • a nickel plating layer as a base is formed on the surface of the resin substrate or resin fine particles, and the nickel plating layer A gold plating layer is formed on the surface of the substrate by a substitution gold plating method.
  • substitution gold plating method is performed on the surface of the nickel plating layer, nickel is eluted from the nickel plating layer, and nickel may diffuse into the gold plating layer or nickel may be deposited on the surface of the gold plating layer.
  • nickel diffuses in the gold plating layer or nickel is deposited on the surface of the gold plating layer there is a problem that the conductivity is lowered.
  • it is necessary to perform a heating step when mounting electronic components on the substrate but this heating step causes nickel to elute from the nickel plating layer, resulting in a decrease in conductivity. was there.
  • Patent Document 1 discloses a method in which a palladium plating layer is formed on the surface of a nickel plating layer by an electroless plating method, and further a gold plating layer is formed on the surface by a displacement gold plating method. . According to this method, by covering the nickel plating layer with a palladium plating layer, nickel is eluted from the nickel plating layer during the replacement gold plating method or during the heating step, and nickel diffuses into the gold plating layer, It is said that nickel can be prevented from being deposited on the surface of the gold plating layer.
  • an electroless palladium plating bath containing a palladium compound and hypophosphorous acid or hypophosphite as a reducing agent is used to deposit a palladium plating layer on the surface of the nickel plating layer by an electroless plating method.
  • a method of forming is disclosed.
  • the palladium plating layer formed by such a method has an amorphous structure due to the phosphorus derived from the reducing agent, the resulting plated structure has a problem of low conductivity.
  • Patent Document 3 uses formic acid or the like as a reducing agent, A method is described in which a palladium plating layer is formed on the surface of a nickel plating layer by an electroless plating method. However, although the method described in Patent Document 3 can form a palladium plating layer on the surface of the nickel plating layer, the conductivity of the resulting plated structure is not sufficient.
  • the conventional plating method has a problem that even if a palladium plating layer can be formed on the surface of a base plating layer such as a nickel plating layer, the resulting plated structure has low conductivity. Therefore, a plating structure in which the crystal structure of the palladium plating layer is not an amorphous structure but excellent in conductivity, and a plating structure in which the purity of palladium in the palladium plating layer is extremely high even when the reduced palladium plating method is used, and excellent in conductivity. There was a need for a method that could produce a body. JP 2007-9305 A JP 2007-92092 A Japanese Patent No. 3051683
  • An object of this invention is to provide the plating structure which implement
  • the present invention is a plating structure in which a palladium plating layer is formed on the surface of a metal substrate, and the palladium plating layer has a crystal orientation ratio of 45 to 60 on the (111) plane measured by an X-ray diffraction method. %, And the total of the crystal orientation ratio of the (200) plane and the crystal orientation ratio of the (220) plane is 40 to 55%.
  • the present invention is described in detail below.
  • the present inventor in a plating structure having a palladium plating layer on the surface of a metal substrate, the crystal orientation ratio of the (111) plane, (200) plane, and (220) plane of the palladium plating layer is within a predetermined range. As a result, it was found that a plated structure having extremely excellent conductivity can be obtained, and the present invention has been completed.
  • the plating structure of the present invention has a palladium plating layer on the surface of a metal substrate.
  • the metal which comprises the said metal base material is not specifically limited, For example, gold
  • the metal substrate may be a metal substrate made of only metal or a metal substrate in which a metal layer is formed on the surface of a non-metal substrate.
  • the metal substrate is a metal substrate in which a metal layer is formed on the surface of a non-metal substrate
  • the metal layer may be formed on the entire surface of the non-metal substrate, and the metal layer is only partially on the surface. It may be formed.
  • the metal layer may be a metal layer made of only a single metal such as nickel or copper, an alloy of nickel or copper and another metal, or a metal containing a substance other than a metal such as phosphorus or boron. It may be a layer. Especially, it is preferable that it is a metal layer containing nickel or copper.
  • the preferable lower limit of the thickness of the metal layer is 20 nm, and the preferable upper limit is 5000 nm.
  • the thickness of the metal layer is less than 20 nm, the adhesion between the metal substrate and the palladium plating layer may be lowered. If the thickness of the metal layer exceeds 5000 nm, the conductivity of the resulting plated structure may be reduced.
  • the metal layer can be formed by, for example, a method of performing electroless plating or electrolytic plating on the non-metallic substrate according to a conventionally known method.
  • the non-metallic substrate is not particularly limited.
  • a resin substrate made of styrene resin, acrylic resin, epoxy resin, polyimide resin, polyethylene terephthalate resin, polycarbonate resin, etc., ceramic substrate made of silica, silicon carbide, etc. And a glass cloth substrate containing an epoxy resin.
  • the shape of the metal substrate is not particularly limited, and examples thereof include a plate substrate, a sheet substrate, and a particulate substrate.
  • the plated structure of the present invention can be used as an electrode for an electronic circuit board or the like.
  • the plated structure of the present invention can be used as conductive fine particles.
  • the metal substrate is preferably fine particles in which a metal layer is formed on the surface of non-metallic fine particles made of an inorganic material or an organic material.
  • non-metallic fine particles made of an inorganic material or an organic material it is possible to impart appropriate elastic modulus, elastic deformability, and restorability to the obtained conductive fine particles.
  • fine particles in which a metal layer is formed on the surface of resin fine particles are more preferable.
  • the resin constituting the resin fine particles is not particularly limited.
  • polyolefin resin acrylic resin, divinylbenzene polymerization resin, divinylbenzene copolymer resin, polyalkylene terephthalate resin, polysulfone resin, polycarbonate resin, polyamide resin, phenol formaldehyde resin,
  • melamine formaldehyde resin benzoguanamine formaldehyde resin
  • urea formaldehyde resin examples include melamine formaldehyde resin, benzoguanamine formaldehyde resin, and urea formaldehyde resin. These resins may be used alone or in combination of two or more.
  • polystyrene resin examples include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyisobutylene, and polybutadiene.
  • acrylic resin examples include polymethyl methacrylate and polymethyl acrylate.
  • divinylbenzene copolymer resin examples include divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer, and divinylbenzene-methacrylic acid ester copolymer.
  • the palladium plating layer may be directly formed on the surface of the metal base material, or may be formed on the surface of the base metal layer formed on the metal base material.
  • the base metal layer may be a base metal layer made of only a single metal such as nickel or copper, and contains an alloy of nickel or copper and another metal, or a substance other than a metal such as phosphorus or boron.
  • An underlying metal layer may be used. Especially, it is preferable that it is a base metal layer containing nickel or copper.
  • the base metal layer can be formed by a method of performing electroless plating or electrolytic plating on the metal substrate according to a conventionally known method.
  • a preferable lower limit of the thickness of the base metal layer is 20 nm, and a preferable upper limit is 5000 nm.
  • the thickness of the base metal layer is less than 20 nm, the adhesion between the metal substrate and the palladium plating layer may be lowered.
  • the thickness of the base metal layer exceeds 5000 nm, the conductivity of the resulting plated structure may be lowered.
  • the palladium plating layer has a (111) plane crystal orientation ratio of 45 to 60% as measured by X-ray diffraction.
  • a palladium plating layer having extremely excellent conductivity can be formed.
  • the crystal orientation ratio of the (111) plane is less than 45%, the crystal orientation ratio of the (220) plane described later increases, so that the corrosion resistance of the plated structure may decrease. Since the crystal orientation rate of the (200) plane, which will be described later, decreases, the conductivity of the plated structure may decrease.
  • the preferable lower limit of the crystal orientation ratio of the (111) plane is 50%, and the preferable upper limit is 55%.
  • the crystal orientation ratio of the (111) plane is the ratio of the diffraction peak intensity of the (111) plane to the total diffraction peak intensity from each crystal plane when using Cu—K ⁇ rays in the X-ray diffraction method. It is a numerical value expressed in percentage.
  • the crystal orientation ratio of the (111) plane can be measured using a sample horizontal X-ray diffractometer for thin film evaluation (“Smart Lab” manufactured by Rigaku Corporation).
  • the palladium plating layer has a total of 40 to 55% of the crystal orientation rate of the (200) plane and the crystal orientation rate of the (220) plane measured by the X-ray diffraction method.
  • the conductivity of the plated structure may be reduced.
  • the corrosion resistance of the structure may be reduced.
  • the preferable lower limit of the sum of the crystal orientation ratio of the (200) plane and the crystal orientation ratio of the (220) plane is 45%, and the preferable upper limit is 50%.
  • the crystal orientation ratio of the (200) plane is The crystal orientation rate of the (220) plane can be an arbitrary numerical value.
  • the sum of the crystal orientation ratio of the (200) plane and the crystal orientation ratio of the (220) plane is the diffraction peak intensity from each crystal plane when using Cu—K ⁇ rays in the X-ray diffraction method. It is a numerical value indicating the ratio of the sum of the diffraction peak intensities of the (200) plane and (220) plane with respect to the sum in percentage.
  • the sum of the crystal orientation ratio of the (200) plane and the crystal orientation ratio of the (220) plane is measured using a sample horizontal X-ray diffractometer for thin film evaluation (“Smart Lab” manufactured by Rigaku Corporation). be able to.
  • a preferable lower limit of the purity of palladium in the palladium plating layer is 95% by weight.
  • the conductivity and corrosion resistance of the resulting plated structure may be lowered.
  • the more preferable lower limit of the purity of palladium in the palladium plating layer is 96% by weight, the still more preferable lower limit is 97% by weight, and the particularly preferable lower limit is 99% by weight.
  • the purity of palladium in the palladium plating layer can be measured using an energy dispersive X-ray spectrometer (EDS) or an ICP emission analyzer.
  • the thickness of the said palladium plating layer is not specifically limited, A preferable minimum is 10 nm and a preferable upper limit is 1000 nm. By setting the thickness of the palladium plating layer within the range of 10 to 1000 nm, it is possible to form a palladium plating layer with extremely excellent conductivity.
  • a more preferable lower limit of the thickness of the palladium plating layer is 100 nm, a more preferable upper limit is 800 nm, a still more preferable lower limit is 200 nm, and a further preferable upper limit is 500 nm.
  • the palladium plating layer may be formed on the outermost surface of the plating structure of the present invention, and a conductive layer such as a gold layer may be further formed on the surface of the palladium plating layer.
  • the method for producing the plated structure of the present invention is not particularly limited.
  • formic acid or formate (hereinafter also referred to as reducing agent 1) as a reducing agent, and a catalyst on the surface of the metal substrate.
  • reducing agent 2 a palladium plating solution containing a reducing agent having an action
  • the palladium plating solution can be manufactured by a method of appropriately adjusting the pH and the like of the palladium plating solution (hereinafter also simply referred to as “plating structure manufacturing method”).
  • platting structure manufacturing method By the method for producing a plated structure, a palladium plated layer having extremely high palladium purity and excellent conductivity can be formed.
  • the reducing agent having a catalytic action on the surface of the metal substrate does not contain formic acid or formate.
  • the manufacturing method of the plating structure is a reduction plating method using the reducing agent 1 and the reducing agent 2 in combination as a reducing agent.
  • the method for manufacturing a plated structure includes a step of immersing the metal base in a palladium plating solution.
  • the palladium plating solution contains a reducing agent 1 and a reducing agent 2 as a palladium compound and a reducing agent.
  • the palladium compound is not particularly limited, and examples thereof include palladium chloride, sodium palladium chloride, tetraamminechloropalladium, dichlorotetraamminepalladium, dinitrotetraamminepalladium, palladium sulfate, palladium acetate, and palladium nitrate.
  • the concentration of the palladium compound in the palladium plating solution is not particularly limited, but a preferable lower limit is 0.0001 mol / L and a preferable upper limit is 0.5 mol / L.
  • concentration of the palladium compound is less than 0.0001 mol / L, the deposition rate of the palladium plating layer becomes slow, and a palladium plating layer having a sufficient thickness may not be formed. Even if added, the deposition rate of the palladium plating layer may not be improved.
  • the reducing agent 1 is formic acid or formate.
  • the formate include sodium formate, potassium formate, and ammonium formate. These formates may be used alone or in combination of two or more. Of these, sodium formate is preferred. Moreover, you may use the said formic acid and the said formate together.
  • the reducing agent 1 has a role of growing a palladium plating layer starting from palladium deposited on the surface of the metal substrate in the palladium plating solution.
  • a palladium plating layer is formed on the surface of the metal substrate using a palladium plating solution containing only the reducing agent 1, the metal present on the surface of the metal substrate is eluted, and the purity of palladium in the palladium plating layer is Or a uniform palladium plating layer may not be formed on the surface of the metal substrate. Therefore, when a palladium plating solution containing only the reducing agent 1 as the reducing agent is used, the conductivity of the resulting plated structure may be reduced.
  • concentration of the reducing agent 1 in the said palladium plating liquid is not specifically limited, A preferable minimum is 5 g / L and a preferable upper limit is 250 g / L. If the concentration of the reducing agent 1 is less than 5 g / L, sufficient reducibility may not be obtained and a palladium plating layer may not be formed. When the concentration of the reducing agent 1 exceeds 250 g / L, the palladium plating solution may be decomposed or the specified crystal orientation ratio may not be obtained.
  • the concentration of the reducing agent 1 in the palladium plating solution is preferably in the range of 5 to 30 g / L. When the shape of the metal substrate is a fine particle substrate, the concentration of the reducing agent 1 in the palladium plating solution is preferably in the range of 5 to 250 g / L.
  • the reducing agent 2 is not particularly limited as long as it has a catalytic action on the surface of the metal substrate and is a reducing agent other than the reducing agent 1, and examples thereof include sodium hypophosphite, hypophosphorous acid, Examples include dimethylamine borane (DMAB), sodium borohydride, formaldehyde, ascorbic acid, isoascorbic acid, catechol, pyrogallol, and glyoxylic acid. Of these, sodium hypophosphite, hypophosphorous acid, sodium borohydride, formaldehyde, and dimethylamine borane are preferable, and sodium hypophosphite, hypophosphorous acid, formaldehyde, and dimethylamine borane are more preferable.
  • DMAB dimethylamine borane
  • sodium hypophosphite, hypophosphorous acid, sodium borohydride, formaldehyde, and dimethylamine borane are preferable, and sodium hypophosphite, hypophosphorous acid, formaldehyde, and
  • the reducing agent 2 has a role of precipitating palladium serving as a starting point of the palladium plating layer on the surface of the metal substrate in the palladium plating solution.
  • a palladium plating layer is formed on the surface of the metal substrate using a palladium plating solution containing only the reducing agent 2 as a reducing agent, the purity of palladium in the palladium plating layer is reduced, or the palladium plating layer has an amorphous structure. It may become. Therefore, when a palladium plating solution containing only the reducing agent 2 as a reducing agent is used, the conductivity of the plated structure may be lowered.
  • the concentration of the reducing agent 2 in the palladium plating solution is not particularly limited, but a preferable lower limit is 0.05 g / L, and a preferable upper limit is 1.5 g / L. If the concentration of the reducing agent 2 is less than 0.05 g / L, a palladium plating layer having a sufficient thickness may not be formed. If the concentration exceeds 1.5 g / L, decomposition of the palladium plating solution occurs and plating cannot be performed. Or the conductivity of the plated structure may be reduced.
  • a more preferable lower limit of the concentration of the reducing agent 2 is 0.1 g / L, and a more preferable upper limit is 0.5 g / L.
  • the concentration of the reducing agent 1 is 5 to 250 g / L, and the concentration of the reducing agent 2 is 0.05 to 1.5 g. It is preferable to use a palladium plating solution that is / L. In particular, it is more preferable to use a palladium plating solution in which the concentration of the reducing agent 1 is 5 to 250 g / L and the concentration of the reducing agent 2 is 0.1 to 0.5 g / L.
  • a palladium plating layer having a crystal orientation ratio of (111) plane exceeding 60% may be formed. Further, when the concentration of the reducing agent 2 in the palladium plating solution exceeds 1.5 g / L and the concentration of the reducing agent 1 in the palladium plating solution is less than three times the concentration of the reducing agent 2 (111 ) A palladium plating layer having a crystal orientation ratio of less than 45% may be formed.
  • the palladium plating solution preferably further contains a stabilizer, alcohol, complexing agent, pH adjusting agent, buffering agent and the like.
  • a stabilizer at least one of ammonia and an amine compound is used.
  • the amine compound include monoamines such as methylamine, ethylamine, propylamine, trimethylamine, and dimethylethylamine, diamines such as methylenediamine, ethylenediamine, tetramethylenediamine, and hexamethylenediamine, and polyamines such as diethylenetriamine and pentaethylenehexamine.
  • Other amines include ethylenediaminetetraacetic acid, nitrilotriacetic acid, various ammonium salts, potassium salts, sodium salts, and the like.
  • the alcohol has an effect of improving wettability and promoting reduction.
  • examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, ethylene glycol, glycerin and the like.
  • the complexing agent is not particularly limited, and examples thereof include mercaptosuccinic acid and 2-aminopyridine.
  • the pH adjuster is not particularly limited, and examples thereof include sodium hydroxide and ammonia.
  • the pH of the palladium plating solution is not particularly limited, but is preferably pH 7 or more and particularly preferably pH 7 to 10 in order to suppress metal elution from the metal layer or the base metal layer.
  • the buffer is not particularly limited, and examples thereof include ammonium hydrogen phosphate.
  • the palladium plating solution may further contain propionic acid, butyric acid, isobutyric acid, succinic acid, acetic acid, malonic acid, succinic acid, malic acid, tartaric acid, citric acid and ammonium salts, potassium salts, sodium salts, and the like thereof. preferable.
  • the temperature of the palladium plating solution when producing a plating structure using the palladium plating solution is particularly high as long as it can increase the driving force of the plating reaction and does not cause decomposition of the palladium plating solution.
  • a preferable lower limit is 40 ° C and a preferable upper limit is 60 ° C.
  • Example 1 A commercially available pure copper plate (length 4 cm ⁇ width 2 cm ⁇ thickness 0.5 cm, 36 g) was degreased with a 10% by weight aqueous solution of sodium hydroxide and then washed with water. Next, after etching with a hydrogen peroxide-sulfuric acid aqueous solution, the smut was removed with a 10% by weight aqueous solution of sulfuric acid and washed with water to obtain a pure copper plate whose surface was activated.
  • the obtained pure copper plate was immersed in a 1% by weight palladium chloride aqueous solution adjusted to pH 2, and a palladium film was substituted and deposited on the copper surface.
  • the obtained pure copper plate on which the palladium coating is formed is immersed in a palladium plating solution (pH 7.5) having the following composition at a liquid temperature of 50 ° C. for 2 minutes to perform an electroless plating reaction.
  • a plated structure having a 200 nm palladium plated layer was obtained.
  • Palladium plating solution composition Palladium sulfate 0.6g / L Ethylenediamine 20g / L Sodium formate 5g / L (Reducing agent 1) Sodium hypophosphite 0.1 g / L (reducing agent 2) Stabilizer 0.006g / L
  • Examples 2 to 4 Comparative Examples 1 to 4
  • a plated structure was obtained in the same manner as in Example 1 except that the concentrations of the reducing agent 1 and the reducing agent 2 contained in the palladium plating solution were changed to the compositions shown in Table 1.
  • Example 5 A commercially available pure copper plate (length 4 cm ⁇ width 2 cm ⁇ thickness 0.5 cm, 36 g) was degreased with a 10% by weight aqueous solution of sodium hydroxide and then washed with water. Next, after etching with a hydrogen peroxide-sulfuric acid aqueous solution, the smut was removed with a 10% by weight aqueous solution of sulfuric acid and washed with water to obtain a pure copper plate whose surface was activated.
  • the obtained pure copper plate was immersed in a 1% by weight palladium chloride aqueous solution adjusted to pH 2 to displace and deposit a palladium film on the copper surface.
  • the obtained pure copper plate on which the palladium coating is formed is immersed in a base plating solution (pH 5.5) having the following composition at a liquid temperature of 90 ° C. to conduct an electroless plating reaction, thereby having a thickness of 500 nm on the surface.
  • a nickel-phosphorus layer was formed.
  • Palladium plating solution composition Palladium sulfate 0.6g / L Ethylenediamine 20g / L Sodium formate 7g / L (Reducing agent 1) Sodium hypophosphite 0.15 g / L (reducing agent 2) Stabilizer 0.006g / L
  • Example 6 Comparative Examples 5 to 8
  • a plated structure was obtained in the same manner as in Example 4 except that the concentrations of reducing agent 1 and reducing agent 2 contained in the palladium plating solution and the reducing agent species were changed to the compositions shown in Table 2.
  • a palladium plating solution pH 7.5, solution temperature 50 ° C.
  • Example 6 Dinitrotetraammine palladium 2 g / L EDTA 5g / L Sodium formate 10 g / L (reducing agent 1) DMAB (dimethylamine borane) 0.3 g / L (reducing agent 2) Stabilizer 0.03g / L
  • Example 9 A commercially available resin base material (“MCL-E-67” manufactured by Hitachi Chemical Co., Ltd.) was cut into 4 cm long ⁇ 2 cm wide ⁇ 0.5 cm thick and heated at 200 ° C. for 6 hours. Next, the resin substrate was degreased with a 10% by weight aqueous solution of sodium hydroxide and then washed with water. Next, after etching with a hydrogen peroxide-sulfuric acid aqueous solution, the smut was removed with a 10% by weight sulfuric acid aqueous solution and washed with water to obtain a resin substrate whose surface was activated.
  • MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.
  • the obtained resin base material was immersed in a 1% by weight palladium chloride aqueous solution adjusted to pH 2 to displace and deposit a palladium film on the surface of the resin base material.
  • the obtained resin base material on which the palladium coating is formed is immersed in a base plating solution (pH 5.5) having the following composition at a liquid temperature of 90 ° C. to conduct an electroless plating reaction, whereby a thickness of 500 nm is formed on the surface.
  • a nickel-phosphorus layer was formed.
  • Palladium plating solution composition Palladium sulfate 0.6g / L Ethylenediamine 20g / L Sodium formate 5g / L (Reducing agent 1) Sodium hypophosphite 0.15 g / L (reducing agent 2) Stabilizer 0.006g / L
  • Example 10 to 12 Comparative Examples 9 to 12
  • a plated structure was obtained in the same manner as in Example 9, except that the concentrations of reducing agent 1 and reducing agent 2 and the reducing agent species contained in the palladium plating solution were changed to the compositions shown in Table 3.
  • a palladium plating solution pH 7.5, solution temperature 50 ° C.
  • Example 13 A commercially available resin base material (“MCL-E-67” manufactured by Hitachi Chemical Co., Ltd.) was cut into 4 cm long ⁇ 2 cm wide ⁇ 0.5 cm thick and heated at 200 ° C. for 6 hours. Next, the resin substrate was degreased with a 10% by weight aqueous solution of sodium hydroxide and then washed with water. Next, after etching with a hydrogen peroxide-sulfuric acid aqueous solution, the smut was removed with a 10% by weight sulfuric acid aqueous solution and washed with water to obtain a resin substrate whose surface was activated.
  • MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.
  • the obtained resin base material was immersed in a 1% by weight palladium chloride aqueous solution adjusted to pH 2 to displace and deposit a palladium film on the surface of the resin base material.
  • the obtained resin base material on which the palladium film is formed is immersed in a base plating solution (pH 5.5) having the following composition at a liquid temperature of 40 ° C. to conduct an electroless plating reaction, whereby a thickness of 500 nm is formed on the surface.
  • a copper layer was formed.
  • the resin base material on which the obtained copper layer is formed is immersed in a palladium plating solution (pH 7.5) having the following composition at a liquid temperature of 50 ° C. for 2 minutes to perform an electroless plating reaction, thereby producing a surface.
  • a plated structure in which a palladium plating layer having a thickness of 200 nm was formed was obtained.
  • Palladium plating solution composition Palladium sulfate 0.6g / L Ethylenediamine 20g / L Sodium formate 7g / L (Reducing agent 1) Sodium hypophosphite 0.1 g / L (reducing agent 2) Stabilizer 0.006g / L
  • Example 14 to 16 Comparative Examples 13 to 16
  • a plated structure was obtained in the same manner as in Example 13 except that the concentrations of reducing agent 1 and reducing agent 2 contained in the palladium plating solution and the reducing agent species were changed to the compositions shown in Table 4.
  • a palladium plating solution pH 7.5, solution temperature 50 ° C.
  • Example 17 Styrene resin fine particles having an average particle diameter of 4 ⁇ m were immersed in a 10 wt% solution of an ion adsorbent for 5 minutes. Subsequently, the styrene resin fine particles immersed in the ion adsorbent were immersed in an aqueous 0.01 wt% palladium sulfate solution for 5 minutes. Further, dimethylamine borane was added for reduction, filtration, and washing to obtain styrene resin fine particles carrying palladium.
  • a suspension was prepared by mixing 500 mL aqueous solution of ion-exchanged water containing 1% by weight of sodium succinate and 10 g of styrene resin fine particles carrying palladium. Sulfuric acid was added to this suspension to adjust the pH of the suspension to 5. Next, a plating solution containing 20% by weight of nickel sulfate, 20% by weight of sodium hypophosphite, and 8% by weight of sodium hydroxide was prepared. The suspension was brought to 80 ° C., a plating solution was continuously added dropwise to the suspension, and the mixture was stirred for 20 minutes to cause a plating reaction to obtain styrene resin fine particles having a nickel-phosphorus layer having a thickness of 500 nm.
  • Example 18 Comparative Examples 17 to 19
  • a plating structure (conductive fine particles) was obtained in the same manner as in Example 17 except that the concentrations of reducing agent 1 and reducing agent 2 contained in the palladium plating solution and the reducing agent species were changed to the compositions shown in Table 5. .
  • Example 21 Styrene resin fine particles having an average particle diameter of 4 ⁇ m were immersed in a 10 wt% solution of an ion adsorbent for 5 minutes. Subsequently, the styrene resin fine particles immersed in the ion adsorbent were immersed in an aqueous 0.01 wt% palladium sulfate solution for 5 minutes. Further, dimethylamine borane was added for reduction, filtration, and washing to obtain styrene resin fine particles carrying palladium.
  • a suspension was prepared by mixing 500 mL aqueous solution of ion-exchanged water containing 1% by weight of sodium succinate and 10 g of styrene resin fine particles carrying palladium. Sulfuric acid was added to this suspension to adjust the pH of the suspension to 5. Next, a plating solution containing 20% by weight of copper sulfate, 10% by weight of formaldehyde, and 8% by weight of sodium hydroxide was prepared. The suspension was brought to 40 ° C., the plating solution was continuously dropped into the suspension, and the mixture was stirred for 20 minutes to cause a plating reaction, thereby obtaining styrene resin fine particles on which a copper layer having a thickness of 500 nm was formed.
  • the obtained styrene resin fine particles on which the copper layer is formed are immersed in a palladium plating solution (pH 9.0) having the following composition at a liquid temperature of 55 ° C. for 2 minutes to perform an electroless plating reaction.
  • a plated structure (conductive fine particles) having a palladium plating layer with a thickness of 200 nm formed thereon was obtained.
  • Palladium plating solution composition Dichlorotetraammine palladium 5g / L Diethylenetriamine 5g / L Sodium formate 10 g / L (reducing agent 1) Hypophosphorous acid 0.1 g / L (reducing agent 2) Stabilizer 0.003g / L Heavy metal additive 0.2g / L
  • Example 22 to 24, Comparative Examples 20 to 22 A plating structure (conductive fine particles) was obtained in the same manner as in Example 21 except that the concentrations of reducing agent 1 and reducing agent 2 contained in the palladium plating solution and the reducing agent species were changed to the compositions shown in Table 6. .
  • volume resistivity measurement For the plated structures obtained in Examples 1 to 16 and Comparative Examples 1 to 16, a volume resistivity meter (manufactured by Dia Instruments Co., Ltd.) was used to compress 20 kN at the time of 20 kN compression. Volume resistivity was measured. In addition, with respect to the plated structures (conductive fine particles) obtained in Examples 17 to 24 and Comparative Examples 17 to 22, 2.0 g of conductive fine particles were weighed, and a minute compression electric resistance measuring instrument (Shimadzu) was measured by a four-terminal method. Volume resistivity at 20 kN compression was measured using “PCT-200” manufactured by Seisakusho.

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Abstract

L'invention porte sur une structure plaquée ayant une conductivité extrêmement élevée. De façon spécifique, l'invention porte sur une structure plaquée comportant une couche de placage en palladium formée sur la surface d'une base métallique. Dans la couche de placage en palladium, le taux d'orientation cristalline du plan (111), mesuré par diffraction aux rayons X, est de 45 à 60 %, et le total du taux d'orientation cristalline du plan (200) et du taux d'orientation cristalline du plan (220) est de 40 à 55 %.
PCT/JP2009/051798 2008-02-04 2009-02-03 Structure plaquée WO2009099067A1 (fr)

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JP2011159471A (ja) * 2010-01-29 2011-08-18 Nippon Chem Ind Co Ltd 導電性粉体及びそれを含む導電性材料並びに導電性粒子の製造方法
JP2013001995A (ja) * 2011-06-22 2013-01-07 Nippon Chem Ind Co Ltd 導電性粒子の製造方法
US20130130059A1 (en) * 2011-11-17 2013-05-23 Tdk Corporation Coating and electronic component
JP2013108170A (ja) * 2011-11-21 2013-06-06 Samsung Electro-Mechanics Co Ltd 無電解パラジウムめっき液
JP2013127115A (ja) * 2011-11-17 2013-06-27 Tdk Corp 被覆体及び電子部品
JP2015225926A (ja) * 2014-05-27 2015-12-14 Tdk株式会社 電子部品内蔵基板
JPWO2015141485A1 (ja) * 2014-03-17 2017-04-06 日立金属株式会社 触媒用Ｐｄ粒子および触媒用Ｐｄ粉体、触媒用Ｐｄ粒子の製造方法
JP2017538867A (ja) * 2014-12-17 2017-12-28 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ パラジウム無電解めっき用のめっき浴組成物およびパラジウムの無電解めっき方法
JP2022123819A (ja) * 2021-02-12 2022-08-24 松田産業株式会社 パラジウムめっき液及びパラジウムめっき補充液

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KR101704856B1 (ko) * 2010-03-08 2017-02-08 세키스이가가쿠 고교가부시키가이샤 도전성 입자, 이방성 도전 재료 및 접속 구조체
JP5552934B2 (ja) * 2010-07-20 2014-07-16 Ｔｄｋ株式会社 被覆体及び電子部品
WO2014098064A1 (fr) * 2012-12-21 2014-06-26 奥野製薬工業株式会社 Bain formant un film de revêtement conducteur
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JP6932860B1 (ja) 2019-10-30 2021-09-08 古河電気工業株式会社 摺動接点用金属材料およびその製造方法ならびにモータ用ブラシ材および振動モータ

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011159471A (ja) * 2010-01-29 2011-08-18 Nippon Chem Ind Co Ltd 導電性粉体及びそれを含む導電性材料並びに導電性粒子の製造方法
JP2013001995A (ja) * 2011-06-22 2013-01-07 Nippon Chem Ind Co Ltd 導電性粒子の製造方法
US20130130059A1 (en) * 2011-11-17 2013-05-23 Tdk Corporation Coating and electronic component
JP2013127114A (ja) * 2011-11-17 2013-06-27 Tdk Corp 被覆体及び電子部品
JP2013127115A (ja) * 2011-11-17 2013-06-27 Tdk Corp 被覆体及び電子部品
US9177687B2 (en) * 2011-11-17 2015-11-03 Tdk Corporation Coating and electronic component
JP2013108170A (ja) * 2011-11-21 2013-06-06 Samsung Electro-Mechanics Co Ltd 無電解パラジウムめっき液
JPWO2015141485A1 (ja) * 2014-03-17 2017-04-06 日立金属株式会社 触媒用Ｐｄ粒子および触媒用Ｐｄ粉体、触媒用Ｐｄ粒子の製造方法
JP2015225926A (ja) * 2014-05-27 2015-12-14 Tdk株式会社 電子部品内蔵基板
JP2017538867A (ja) * 2014-12-17 2017-12-28 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ パラジウム無電解めっき用のめっき浴組成物およびパラジウムの無電解めっき方法
JP2022123819A (ja) * 2021-02-12 2022-08-24 松田産業株式会社 パラジウムめっき液及びパラジウムめっき補充液

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