WO2007119417A1 - Poudre conductrice métallisée par métallisation sans courant et procédé servant à produire celle-ci - Google Patents

Poudre conductrice métallisée par métallisation sans courant et procédé servant à produire celle-ci Download PDF

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Publication number
WO2007119417A1
WO2007119417A1 PCT/JP2007/055497 JP2007055497W WO2007119417A1 WO 2007119417 A1 WO2007119417 A1 WO 2007119417A1 JP 2007055497 W JP2007055497 W JP 2007055497W WO 2007119417 A1 WO2007119417 A1 WO 2007119417A1
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Prior art keywords
powder
electroless plating
core
nickel
melamine resin
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PCT/JP2007/055497
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English (en)
Japanese (ja)
Inventor
Masaaki Oyamada
Yasuhiro Abe
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Nippon Chemical Industrial Co., Ltd
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Application filed by Nippon Chemical Industrial Co., Ltd filed Critical Nippon Chemical Industrial Co., Ltd
Priority to CN2007800119038A priority Critical patent/CN101415863B/zh
Priority to KR1020087023517A priority patent/KR101305574B1/ko
Publication of WO2007119417A1 publication Critical patent/WO2007119417A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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

Definitions

  • the present invention relates to a conductive electroless plating powder and a method for producing the same.
  • an aminosilane compound, a glycol compound, a nitrile compound, a titanate compound, a butadiene polymer, and linoleic acid are used as a synthetic resin material.
  • Unsaturated fatty acids such as linolenic acid, etc.
  • a method is proposed in which the synthetic resin material is coated with a selected noble metal-capturing surface treatment material to carry noble metal ions, and then electroless plating is performed. .
  • Patent Document 1 In the method described in Patent Document 1, it is difficult to obtain a material having excellent adhesiveness particularly for fine particles having an average particle diameter of 20 ⁇ m or less. Difficult to use.
  • Patent Document 1 Japanese Patent Laid-Open No. 61-64882
  • the object of the present invention is to provide a conductive material having excellent adhesion without using chromic acid, permanganic acid, or the like, which causes environmental pollution, especially fine particles having an average particle diameter of 20 ⁇ m or less.
  • Means for solving the problem [0007]
  • the present invention provides a conductive electroless plating powder characterized in that the surface of the core powder is coated with melamine resin and a metal film is formed by electroless plating. By doing so, the above-mentioned purpose is achieved.
  • the conductive electroless plating powder of the present invention (hereinafter also simply referred to as a platter powder) is obtained by coating the surface of the core material powder with melamine resin and further forming a metal film by electroless platter. It will be.
  • the surface of the core material powder may be hydrophobic or hydrophilic.
  • the method of the present embodiment is particularly effective for the core material powder having a hydrophobic surface.
  • the core powder is preferably substantially insoluble in water, and more preferably does not dissolve or change in acid or alkali.
  • the shape of the core powder is not particularly limited.
  • the core powder can be in the form of a powder, but other shapes such as fibers, hollows, plates, and needles can be used. It may be a thing.
  • a spherical one is particularly preferable in that it has excellent filling properties when used as a conductive filler.
  • the core material powder as an inorganic substance, metal (including an alloy), glass, ceramics
  • Silica carbon, metal or non-metal oxides (including hydrates), metal silicates including aluminosilicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, metal phosphates, Examples thereof include metal sulfides, metal acid salts, metal halides, and carbon.
  • Organic substances include natural fiber, natural resin, polyethylene, polypropylene, polychlorinated butyl, polystyrene, polybutene, polyamide, polyacrylic acid ester, polyacrylic nitrile, polyacetal, ionomer, polyester and other thermoplastic resin, alkyd
  • the resin include resin, phenol resin, urea resin, benzoguanamine resin, melamine resin, xylene resin, silicone resin, epoxy resin, and diallyl phthalate resin. These may be used alone or as a mixture of two or more.
  • the average particle size is 0.5 to 100. ⁇ m, especially 0.8 to 80 ⁇ m, especially 1 to 20 ⁇ m suppresses agglomeration during the plating process, and is particularly effective from the viewpoint of adapting to a narrow pitch as electroconductive particles after electroless plating. Preferred.
  • the average particle diameter of core material powder shows the value measured using the electrical resistance method.
  • the particle size distribution of the core material powder measured by the method described above has a range.
  • the width of the particle size distribution of the powder is represented by a coefficient of variation represented by the following calculation formula (1).
  • Coefficient of variation (%) (standard deviation Z average particle size) X 100 Formula (1)
  • a large coefficient of variation indicates that there is a range of distribution, while a small coefficient of variation indicates that the particle size distribution is sharp. Indicates that there is.
  • the coating amount of melamine rosin varies depending on the type and shape of the core powder used, but in many cases it is 0.1 to 15% by weight, preferably 0.5 to 10% by weight. desirable.
  • the reason for this is that when the coating amount of melamine resin is less than 0.1% by weight, the coating amount is insufficient and the plating adhesion tends to be difficult to obtain due to excellent plating adhesion. This is because in the step (1) of obtaining the core powder coated with melamine resin, fine particle melamine resin is generated alone and tends to remain as a foreign substance. Further, the melamine rosin may be modified.
  • the metal film in the electroless electroless plating powder is usually a single metal single layer structure. If desired, the metal film may have a multilayer structure of two or more different metals. In addition, the metal film may be crystalline or amorphous depending on the type and staking conditions. Furthermore, the metal film may be magnetic or non-magnetic.
  • the metal here includes not only a simple metal but also an alloy (for example, a nickel-phosphorus alloy or a nickel-boron alloy). Usable metals include Ni, Fe, Cu, Co, Pd, Ag, Au, Pt, and Sn.
  • the thickness of the metal film is preferably 0.001 to 2 ⁇ m, particularly preferably 0.001 to 1 ⁇ m. The thickness of the metal film can be calculated based on the amount of nickel ions added and the chemical analysis ability.
  • Ni is also preferable in terms of economic viewpoint.
  • nickel is used as an example of the metal.
  • the metal that can be used is not limited to this.
  • the production method of the present embodiment includes a step of contacting a core material powder and an initial condensate of melamine resin, and performing a polymerization reaction of the initial condensate to obtain a core material powder coated with melamine resin Next, a step of supporting a noble metal on the surface of the core material powder coated with the melamine resin, and a step of subjecting the core material powder supporting the noble metal to an electroless plating process in the next step.
  • Stable quality plating powder can be advantageously obtained industrially.
  • the core material powder is coated with the melamine resin by bringing the core material powder and the initial condensate of the melamine resin into contact with each other to perform a polymerization reaction of the initial condensate. This is a step of obtaining a core powder.
  • the initial condensate of melamine resin means a product in which a condensation reaction is caused by heating or addition of an acid catalyst to produce melamine resin.
  • the initial condensate of melamine resin may be a commercially available product, or a product obtained by reacting a melamine compound with an aldehyde compound is used as the initial condensate of melamine resin. May be.
  • Examples of the melamine compound include melamine, a melamine compound obtained by substituting hydrogen of an amino group of melamine with an alkyl group, a alkenyl group, or a phenol group (for example, JP 09-1432 38 A). ), Substituted melamine compounds in which the hydrogen of the amino group of melamine is substituted with a hydroxyalkyl group or an aminoalkyl group (for example, see JP-A-5-202157), etc. Melamine is preferred because it is readily available and inexpensive.
  • Some of the melamine compounds are also urea, thiourea, ethylene urea and other ureas, benzoguanamine, acetoguanamine and other guanamines, phenol, cresol, alkylphenol, resorcin, hydroquinone, pyrogallol and other phenols, -It may be substituted with phosphorus.
  • aldehyde compound examples include formaldehyde, paraformaldehyde, acetoaldehyde, benzaldehyde, furfural and the like, and formaldehyde and paraformaldehyde are preferable in terms of reactivity with the melamine compound.
  • the addition amount of the aldehyde compound is 1.1 to 6.0 times mol, preferably 1.2 to 4.0 in terms of a molar ratio to the melamine compound. It is preferred to be double moles.
  • the solvent that can be used is particularly preferably water, but may be used as a mixed solvent of water and an organic solvent.
  • a solvent that can dissolve the initial condensate of melamine resin for example, alcohols such as methanol, ethanol, and propanol, dioxane, tetrahydrofuran, 1
  • Ethers such as 2-dimethoxyethane
  • polar solvents such as dimethylformamide and dimethyl sulfoxide.
  • reaction of the melamine compound and the aldehyde compound is carried out at a pH of 8 to 9. If necessary, the reaction can be carried out by adding a base group.
  • Usable bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and aqueous ammonia can be used as the base that can be used.
  • Reaction temperature is 25-: An initial condensate of melamine rosin having a molecular weight of about 200-700 with LOO can be obtained.
  • the melamine modified with alcohol by reacting the initial condensate of melamine resin with alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol in the presence of a small amount of acidic substance.
  • alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol
  • An initial condensate of rosin can be obtained.
  • the amount of the initial condensate of melamine rosin varies depending on the type of the core powder used, but in many cases is 0.1 to 15% by weight, preferably 0.5 to 10% by weight. It is desirable to do.
  • the reaction operation in the step (1) of obtaining the core material powder coated with melamine rosin comprises preparing a solvent containing the core material powder and adding the solvent to the solvent.
  • a method of adding an initial condensate of melamine resin and performing a polymerization reaction of the initial condensate, and adding the core powder to a solvent containing the initial condensate of melamine resin and polymerizing the initial condensate Method for carrying out reaction, or core material powder, melamine compound and aldehyde compound, a predetermined amount is added, and if necessary, an alkali agent is added and an initial condensate of melamine resin is directly added in a solvent.
  • the method of performing the polymerization reaction can be used.
  • the polymerization reaction may be carried out by adding an acid catalyst if necessary, and the reaction is carried out under heating at 40 to LOO ° C. After completion of the reaction, solid-liquid separation is carried out by a conventional method, followed by drying at 60 to 180 ° C Alternatively, spray-dry the reaction solution as it is and cover with melamine rosin. Covered core powder can be obtained.
  • the acid catalyst that can be used in the polymerization reaction is not particularly limited. 1S
  • hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, alkylbenzenesulfonic acid In addition, sulfonic acids such as sulfamic acid, and organic acids such as formic acid, oxalic acid, benzoic acid, and phthalic acid can be used.
  • the catalytic treatment step (2) noble metal ions are captured by a core material powder that has the ability to capture noble metal ions or that has been provided with a surface treatment. This is a step of reducing this and supporting the noble metal on the surface of the core powder.
  • the core material powder on which the noble metal is supported is dispersed and mixed in the initial thin film forming liquid containing nickel ions, a reducing agent and a complexing agent, and the nickel ions are reduced.
  • the electroless plating process (4) is a process for producing a plating powder having a nickel coating on the surface of the core powder by electroless plating.
  • the core material powder coated with the melamine resin obtained in the step (1) is surface-modified so that the surface thereof has a precious metal ion capturing ability or a precious metal ion capturing ability.
  • the noble metal ions are preferably palladium or silver ions. Having a precious metal ion scavenging ability means that the precious metal ion can be captured as a chelate or salt.
  • the core powder is dispersed in a dilute acidic aqueous solution of a noble metal salt such as palladium chloride or silver nitrate.
  • a noble metal salt such as palladium chloride or silver nitrate.
  • Noble metal salt concentration is sufficient surface area lm 2 per 1 X 10- 7 ⁇ 1 X 10- 2 mol per mol of silver powder.
  • the core powder with the precious metal ions captured is separated from the system and washed with water. Subsequently, the core powder is suspended in water, and a reducing agent is added thereto to reduce the precious metal ions.
  • the noble metal is supported on the surface of the core powder.
  • the reducing agent include sodium hypophosphite, sodium borohydride, potassium borohydride, dimethylamine borane, hydrazine, formalin and the like.
  • a sensitivity treatment for adsorbing tin ions on the powder surface may be performed.
  • the surface-modified core material powder may be put into an aqueous stannous chloride solution and stirred for a predetermined time.
  • the initial thin film forming step is mainly performed for the purpose of smoothing the uniform precipitation of nickel on the core powder.
  • the core powder carrying the noble metal is sufficiently dispersed in water.
  • a shearing dispersion device such as a colloid mill or a homogenizer can be used.
  • a dispersant such as a surfactant can be used as necessary.
  • the aqueous suspension thus obtained is dispersed and mixed in an initial thin film forming liquid containing nickel ions, a reducing agent and a complexing agent. This initiates a nickel ion reduction reaction, and an initial nickel thin film is formed on the surface of the core powder.
  • the initial thin film of nickel to be formed may be thin enough to smooth the surface of the core powder.
  • the thickness of the initial thin film is preferably 0.001 to 2 ⁇ m, particularly preferably 0.001 to 1 ⁇ m.
  • the initial thin film thickness can be calculated from the amount of nickel ions added and the ability to analyze the ions.
  • Tsu Ke concentration Noreion ⁇ or 2. 0 X 10- 4 ⁇ 1 0 Monore / Rittonore, especially 1. 0 X 10 — 3 to 0.1 monolayer / liter is preferable.
  • the nickel ion source a water-soluble nickel salt such as nickel sulfate or nickel chloride is used. From the same viewpoint, it is preferable that the initial concentration ⁇ of the reducing agent in the thin film-forming solution or 4 X 10- 4 ⁇ 2. 0 Monore / Rittonore, especially 2. 0 X 10- 3 ⁇ 0. 2 Monore / liters .
  • the reducing agent those similar to those used for the reduction of the noble metal ions described above can be used.
  • the initial thin film forming liquid preferably contains a complexing agent.
  • the complexing agent is a compound that has a complex forming action on the metal ion to be plated.
  • an organic carboxylic acid or a salt thereof such as citrate, hydroxyacetic acid, tartaric acid, malic acid, lactic acid or dulconic acid or an alkali metal salt or ammonium salt thereof can be used as a complexing agent.
  • amine groups such as glycine, alanine, ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and other amino groups A compound having can also be used. These complexing agents can be used alone or in combination of two or more.
  • the amount of the complexing agent in the initial thin film forming liquid is preferably 0.003 to 10 monole / Ritsunore, particularly 0.006 to 4 monore / Ritsunore! /.
  • the concentration of the core powder in the aqueous suspension is 0.1 to 500 g / liter, particularly 0.5 to 300 g / liter.
  • the aqueous suspension obtained by mixing the aqueous suspension containing the core powder and the initial thin film forming liquid is then subjected to an electroless plating process described later.
  • the ratio of the total surface area of the core powder contained in the aqueous suspension to the volume of the aqueous suspension ( This ratio is generally referred to as the load amount) 0.1 to 15 m 2 / l, especially 1 to LOm 2 / l, which is a point force that can easily form a nickel film with excellent adhesion. preferable.
  • a core powder on which an initial thin film is formed and an aqueous suspension containing the complexing agent (b) a nickel ion-containing liquid, and (c) a reducing agent Use 3 liquids.
  • aqueous suspension (a) the one obtained in the above-described initial thin film forming step may be used as it is.
  • the nickel ion-containing liquid is an aqueous solution of a water-soluble nickel salt such as nickel sulfate or nickel chloride as a nickel ion source.
  • the nickel ion concentration should be 0.1 to 1.2 monolith / lit nore, especially 0.5 to 1.0 monolet / lit nore, and it can easily form a nickel film with excellent strength and adhesion. Preferred from.
  • the nickel ion-containing liquid preferably contains a complexing agent of the same type as the complexing agent contained in the aqueous suspension. That is, it is preferable that the same kind of complexing agent is contained in both the aqueous suspension (a) and the nickel ion-containing liquid (b). This makes it possible to easily form a nickel film having excellent adhesion. The reason for this is not clear, but ( By adding a complexing agent to both the aqueous suspension of a) and the nickel ion-containing liquid of (b), nickel ions are stabilized and the reduction reaction is prevented from proceeding rapidly. It is speculated that it is also the power that can be.
  • the concentration of the complexing agent in the nickel ion-containing liquid (b) affects the formation of the nickel film in the same manner as the concentration of the complexing agent in the aqueous suspension (a).
  • the amount of the complexing agent in the nickel ion-containing liquid is preferably 0.006 to 12 mol Z liter, particularly preferably 0.012 to 8 mol Z liter.
  • the reducing agent-containing liquid (c) is generally an aqueous solution of a reducing agent.
  • a reducing agent those similar to those used for the reduction of the noble metal ions described above can be used. It is particularly preferable to use sodium hypophosphite. Since the concentration of the reducing agent affects the reduction state of nickel ions, it is preferable to adjust the concentration within the range of 0.1 to 20 mol Z liter, particularly 1 to 10 mol Z liter.
  • the nickel ion-containing liquid (b) and the reducing agent-containing liquid (c) are added individually and simultaneously. As a result, nickel ions are reduced, and nickel is deposited on the surface of the core powder to form a film.
  • the addition rate of the nickel ion-containing solution and the reducing agent-containing solution is effective in controlling the nickel deposition rate.
  • the deposition rate of nickel affects the formation of a nickel film with good adhesion. Therefore, it is preferable to control the nickel deposition rate by adjusting the addition rate of both solutions at 1 to: LOOOOnmZ, particularly 5 to 300 nm / hour.
  • the deposition rate of nickel can be obtained by calculation from the addition rate of the nickel ion-containing liquid.
  • the load 0. l ⁇ 15m 2 / l is preferably kept in a range especially of 1 to 10 m 2 / liter.
  • nickel is deposited uniformly.
  • the load amount is within this range when the addition of the two liquids is completed and the reduction of nickel ions is completed! /.
  • the pH of the aqueous suspension is kept in the range of 3 to 13, especially 4 to: Force of water insoluble precipitation of nickel This is preferable from the viewpoint of preventing the formation of products.
  • a predetermined amount of a pH adjusting agent such as sodium hydroxide may be added to the reducing agent-containing solution.
  • the obtained plating powder is separated after filtration and washing several times. Further, as an additional step, a gold-plated layer forming step as the uppermost layer may be performed on the nickel film.
  • the gold plating layer can be formed according to a conventionally known electroless plating method.
  • an electroless plating solution containing tetrasodium ethylenediammine tetraacetate, trisodium citrate and potassium cyanate and adjusted to pH with sodium hydroxide.
  • a gold plating layer is formed on the nickel film.
  • the thickness of the gold plating layer is generally about 0.001 to 0.5 m. The thickness of the gold plating layer can be calculated from the amount of gold ions added and the ability to analyze the ions.
  • the thickness of the nickel film is preferably about 0.005 to 10 / ⁇ ⁇ , particularly about 0.01 to 2 / ⁇ ⁇ .
  • the thickness of the nickel film can be measured, for example, by observation with a scanning electron microscope, and the amount of nickel ion added and the ability to analyze chemistry can also be calculated.
  • the plating powder of the present invention obtained by force is used for connecting, for example, an anisotropic conductive film (ACF), a heat seal connector (HSC), and an electrode of a liquid crystal display panel to a circuit board of an LSI chip for driving. It is suitably used for applications such as conductive materials and polarizing plates.
  • ACF anisotropic conductive film
  • HSC heat seal connector
  • electrode of a liquid crystal display panel to a circuit board of an LSI chip for driving. It is suitably used for applications such as conductive materials and polarizing plates.
  • the slurry was stirred while using ultrasonic waves, and 20 mL of a mixed aqueous solution of 0.117 mol / liter dimethylamine borane and 0.16 mol Z liter boric acid was added thereto.
  • the palladium ion was reduced by stirring for 2 minutes while using ultrasonic waves at room temperature.
  • the aqueous suspension obtained in the initial thin film formation step was mixed with a nickel ion-containing liquid consisting of 0.86 mol ZL of nickel sulfate and 0.17 mol ZL of sodium tartrate and 2.57 mol ZL of hypophosphorous acid.
  • a nickel ion-containing liquid consisting of 0.86 mol ZL of nickel sulfate and 0.17 mol ZL of sodium tartrate and 2.57 mol ZL of hypophosphorous acid.
  • the aqueous suspension was filtered, and the filtrate was washed with repulp three times and dried in a vacuum dryer at 110 ° C. As a result, a plating powder having a nickel lurin alloy plating film was obtained.
  • plating powder was obtained by the same operation except that the step (1) was not performed.
  • Example 1 except that the step (1) was replaced with the following step (1-1), a plated powder was obtained in the same manner as in Examples 1-3.
  • Example 2 10 parts by weight of the same styrene resin used in Example 1 was added to 100 parts by weight of an aqueous solution containing 1.0% by weight of the surface treating agent shown in Table 1, and immersed for 1 hour at room temperature. Next, it was dried at 110 ° C. to prepare a core powder coated with the surface treatment agent.
  • Example 1 a plated powder was obtained in the same manner as in Example 1, except that the step (1) was replaced with the following step (1-2).
  • Chloric anhydride 2.0 mol ZL, sulfuric acid 3.6 mol ZL strength 100 parts by weight of the core powder was charged in 2 L of an etching solution, heated to 70 ° C., and stirred for 10 minutes. Next, filtration and washing were repeated to obtain a core material powder subjected to etching treatment.
  • the thickness of the plating film and the adhesion of the plating film were measured and evaluated for the obtained plating powder by the following method. The results are shown in Table 2. The amount of chromium remaining in the plating powder was measured, and the results are also shown in Table 2.
  • the plating powder was immersed in nitric acid to dissolve the adhesive film, the film components were quantified by ICP or chemical analysis, and the thickness was calculated by the following equation.
  • A W / 100-W Where r is the radius of the core powder m), t is the thickness of the adhesive film m), and d is the adhesive film.
  • the specific gravity of, d is the specific gravity of the core powder, w is the metal content (% by weight).
  • the plating powder was immersed in nitric acid to dissolve the adhesion film, and further sulfuric acid was added for thermal decomposition.
  • the obtained solution strength was also measured by ICP for chromium.
  • N. D. indicates that the detection limit is 0.002 mgZg or less.
  • the plating powders of the respective examples are excellent in adhesion of the adhesive skin film and are substantially free of chromium.
  • the plating powders of Comparative Examples 1 to 6 do not contain chromium, but are easily peeled off.
  • the plating powder of Comparative Example 7 is excellent in the adhesion of the plating film, but chromium is contained in the plating powder.
  • Electroless plating powder can be obtained.
  • the conductive electroless plating powder of the present invention is used for driving, for example, anisotropic conductive film (ACF), heat seal connector (HSC), and electrodes of liquid crystal display panels. It is suitable for use in conductive materials for connecting LSI chip circuit boards and polarizing plates.

Abstract

Poudre conductrice métallisée par métallisation sans courant laquelle, même lorsqu'elle est constituée de fines particules ayant un diamètre moyen de particules, en particulier, inférieur ou égal à 20 µm, a une excellente adhérence du dépôt qui lui est conférée sans utiliser d'acide chromique, lequel est une source de pollution pour l'environnement, d'acide permanganique, entre autres ; et procédé servant à produire industriellement et de façon avantageuse ladite poudre. La poudre conductrice métallisée par métallisation sans courant est caractérisée en ce qu'elle comprend une poudre de base recouverte d'une résine de mélamine et un film de revêtement métallique déposé sur celle-ci par métallisation sans courant. Le procédé est caractérisé en ce qu'il comprend : une étape consistant à mettre en contact la poudre de base avec un produit de condensation initial pour une résine de mélamine et à polymériser le produit de condensation initial pour obtenir une poudre de base recouverte d'une résine de mélamine ; une étape consistant à déposer un métal noble sur la surface de la poudre de base recouverte de la résine de mélamine ; et une étape consistant à métalliser la poudre de base sur laquelle le métal noble est déposé par une métallisation sans courant.
PCT/JP2007/055497 2006-03-28 2007-03-19 Poudre conductrice métallisée par métallisation sans courant et procédé servant à produire celle-ci WO2007119417A1 (fr)

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CN2007800119038A CN101415863B (zh) 2006-03-28 2007-03-19 导电性非电解电镀粉体及其制造方法
KR1020087023517A KR101305574B1 (ko) 2006-03-28 2007-03-19 도전성 무전해 도금 분체 및 그의 제조 방법

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WO2009054386A1 (fr) 2007-10-22 2009-04-30 Nippon Chemical Industrial Co., Ltd. Poudre conductrice revêtue et adhésif conducteur l'utilisant
WO2011158783A1 (fr) * 2010-06-16 2011-12-22 ソニーケミカル＆インフォメーションデバイス株式会社 Particules conductrices, leur procédé de production et adhésif anisotropiquement conducteur
JP5505149B2 (ja) * 2010-06-16 2014-05-28 デクセリアルズ株式会社 導電粒子、その製造方法及び異方性導電接着剤
JP5505156B2 (ja) * 2010-06-30 2014-05-28 デクセリアルズ株式会社 導電粒子、その製造方法及び異方性導電接着剤
JP6352879B2 (ja) * 2015-10-15 2018-07-04 小島化学薬品株式会社 無電解白金めっき液
CN106903305A (zh) * 2017-04-12 2017-06-30 合肥学院 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法

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CN101415863B (zh) 2011-04-20
JP2007262495A (ja) 2007-10-11
KR101305574B1 (ko) 2013-09-09
KR20080111022A (ko) 2008-12-22

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