WO2009017266A1 - Procédé de dépôt autocatalytique de particules polymères réticulées monodispersées à diamètre micronique et particules plaquées correpondantes - Google Patents

Procédé de dépôt autocatalytique de particules polymères réticulées monodispersées à diamètre micronique et particules plaquées correpondantes Download PDF

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Publication number
WO2009017266A1
WO2009017266A1 PCT/KR2007/003683 KR2007003683W WO2009017266A1 WO 2009017266 A1 WO2009017266 A1 WO 2009017266A1 KR 2007003683 W KR2007003683 W KR 2007003683W WO 2009017266 A1 WO2009017266 A1 WO 2009017266A1
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WIPO (PCT)
Prior art keywords
plating
slurry
particles
crosslinked polymer
solution
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PCT/KR2007/003683
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English (en)
Inventor
Dong Ok Kim
Jeong Hee Jin
Won Il Son
Seok Heon Oh
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Hanwha Chemical Corporation
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Publication date
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Priority to PCT/KR2007/003683 priority Critical patent/WO2009017266A1/fr
Publication of WO2009017266A1 publication Critical patent/WO2009017266A1/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
    • 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
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • 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

Definitions

  • the present invention relates to a method for the electroless metal plating of micron- sized monodisperse crosslinked particles and plated particles prepared thereby, and more particularly to a process for the electroless metal plating of micron-sized monodisperse crosslinked particles, which comprises forming a thin continuous metal plating film on micron- sized monodisperse crosslinked particles through electroless plating so as to improve plating uniformity, plating reproducibility and dispersion properties, as well as plated particles prepared thereby.
  • ACF anisotropic conductive film
  • COG chip-on-glass
  • COF chip-on-film
  • FC flip-chip
  • the conductive particles have a double coating structure, in which a conductive metal layer of nickel or copper is plated on insulating core particles (Japanese Patent Laid-Open Publication Nos. Hei 6-96771 and 7-118866 and Japanese Patent No. 2507381), and gold or platinum is additionally plated thereon in order to prevent the oxidation of the metal layer and improve the electrical conductivity of the metal layer (Japanese Patent Laid-Open Publication Nos. Hei 10- 101962 and 11 -329060).
  • base particles for plating polymer materials having a given elasticity have recently been emphasized, rather than inorganic materials.
  • this dropping method forms uniform plating surfaces on crosslinked polymer particles and improves the dispersion of plated particles, because it is easy to control the plating rate, the stability of a plating bath, and the like, compared to a method of introducing crosslinked polymer particles into a plating bath at the same time.
  • this method leaves room for improvement with respect to plating uniformity and plating reproducibility depending on the feed rate of a plating solution and the pH of a plating bath, and also fails to sufficiently improve the dispersion of plated particles.
  • Disclosure [Technical Problem) Accordingly, the present inventors have conducted studies on the electroless metal plating of crosslinked polymer microparticles in order to solve the problems occurring in the prior dropping method.
  • the present inventors have found that plating rate and dispersion conditions at the initial stage of plating have strong effects on plating uniformity, plating reproducibility and dispersion properties in electroless plating, and that the agglomeration of plated particles, which has a great effect on plating yield and particle surface conditions in the metal plating of crosslinked polymer microparticles, occurs predominantly at the initial state of plating, thereby completing the present invention.
  • the present invention provides a process for the electroless metal plating of monodisperse crosslinked polymer microparticles using a dropping method, which can improve plating uniformity and plating reproducibility by adjusting pH at the initial stage of plating and improving a plating solution addition method, as well as plated particles prepared thereby.
  • the present invention provides a process for the electroless metal plating of monodisperse crosslinked polymer microparticles, which can improve the dispersion of plated particles by placing an intermission period, during which the addition of a plating solution is stopped, after the initial stage of plating, carrying out intensive mixing, and then starting the plating reaction again, as well as plated particles prepared thereby.
  • a method for the electroless metal plating of monodisperse crosslinked polymer microparticles which improves plating uniformity, plating reproducibility and dispersion properties, the method comprising the steps of: (i) subjecting crosslinked polymer microparticles to a catalytic process (pretreatment process) with SnCl 2 and PdCl 2 to obtain slurry; (ii) adding the slurry to a plating bath, adjusting the pH of the slurry to a value higher than a normal pH level by about 1-3, and continuously adding a plating solution, divided into a metal salt solution and a reducing agent solution, to the slurry, according to a dropping method; (iii) after a point of time at which the color of the slurry turns black, carrying out an initial stage of plating at said adjusted pH for 1/100-1/5 of a total plating time; and (iv) adjusting the pH of the slurry to the normal
  • a method for electroless metal plating of micron-sized monodisperse crosslinked polymer particles using a dropping method comprising the steps of: (i) subjecting crosslinked polymer microparticles to a catalytic process (pretreatment process) with SnCl 2 and PdCl 2 to obtain slurry; (ii) adding the slurry to a plating bath, adjusting the pH of the slurry to a value higher than a normal pH level by about 1-3, and then simultaneously adding 1/100-1/5 of the amount of metal salt and reducing agent that is to be added over the total plating time; (iii) after a point of time at which the color of the slurry turns black, an initial stage of plating at said adjusted pH for 1/100- 1/5 of the total plating time; and (iv) adjusting the pH of the slurry to the normal pH level, and then adding the plating solution to the slurry to perform the remaining stage of plating.
  • FIG. 1 is a 10,000-fold enlarged SEM (scanning electron microscope) photograph of the surface of plated particles prepared in Example 1.
  • FIG. 2 is a 10,000-fold enlarged SEM photograph of the surface of plated particles prepared in Example 2.
  • FIG. 3 is a 10,000-fold enlarged SEM photograph of the surface of plated particles prepared in Example 3.
  • FIG. 4 is a 10,000-fold enlarged SEM photograph of the surface of plated particles prepared in Example 4.
  • FIG. 5 is a 10,000-fold enlarged SEM photograph of the surface of plated particles prepared in Comparative Example 1.
  • FIG. 6 is a 10,000-fold enlarged SEM photograph of the surface of plated particles prepared in Comparative Example 2. [Best Mode]
  • the present invention provides a method for the electroless metal plating of monodisperse crosslinked polymer microparticles, which can improve plating uniformity, plating reproducibility and dispersion properties, which are problems in the prior process, which includes the use of a dropping method, by 1) adjusting the pH at the initial stage of plating and improving a plating solution addition method at the initial stage of plating, and 2) adding a given intermission after the initial stage of plating, conducting intensive mixing, and then carrying out the plating reaction again, as well as plated particles prepared thereby.
  • the dispersion of plated particles can be improved by placing an intermission of 1/100-1/5 of the total plating time, in which the addition of the metal salt and the reducing agent is stopped, after an initial plating stage, then conducting more intensive mixing compared to the initial stage of plating so as to sufficiently disperse plated particles, which are weakly agglomerated in a relatively initial stage of plating, and then adding the plating solution again.
  • Resin that can be used in the present invention may be one or a mixture of two or more selected from among, for example: polyolefins, such as polyethylene, polyvinyl chloride, polypropylene, polystyrene and polyisobutylene; olefin copolymers, such as styrene- acrylonitrile copolymers and acrylonitrile-butadiene-styrene terpolymers; acrylic acid derivatives, such as poly acrylate, polymethyl methacrylate and polyacrylamide; polyvinyl compounds, such as polyvinyl acetate and polyvinyl alcohol; ether polymers, such as polyacetal, polyethylene glycol, polypropylene glycol and epoxy resin; amino compounds, such as benzoguanamine, urea
  • the average particle size of the resin microparticles is 0.5-1000 jLfliL If the average particle size is less than 0.5 ⁇ m, the resulting conductive particles will not be brought into contact with the electrode surfaces that are to be electrically connected with each other, and thus contact failure will often occur due to the distance between electrodes. On the other hand, if the average particle size is more than 1000 ⁇ m, an electrically conductive fine connection cannot be achieved. For these reasons, the average particle size is limited within the above-specified range.
  • the average particle size is preferably 1-100 ⁇ m, more preferably 1-20 ⁇ m, and most preferably 2-10 ⁇ m.
  • the aspect ratio of the resin microparticles for use in the present invention is less than 2, preferably less than 1.3, and more preferably 1.1. If the aspect ratio is more than 2, there may be a large amount of particles that cannot come into contact with electrode surfaces due to their non-uniform particle size in a process of making electrical contact between electrodes using the resulting conductive particles. For this reason, the aspect ratio is limited within the above- specified range.
  • the coefficient of variation (Cv) of the resin microparticles for use in the present invention is less than 30%, preferably 20%, and more preferably less than 10%. If the coefficient of variation (Cv) is more than 30%, there can be a large amount of particles that cannot come into contact with electrode surfaces due to their non-uniform particle size in a process of making electrical contact between electrodes using the resulting conductive particles. For this reason, the coefficient of variation (Cv) is limited within the above-specified range.
  • the coefficient of variation (Cv) is defined by the following Math Figure 1 :
  • ⁇ is the standard deviation of particle size
  • Dn is number-average particle size.
  • the standard deviation and the number-average particle size can be calculated using a particle size analysis system (Accusizer model 780, Particle Sizing Systems, Inc,).
  • a metal coaling film is formed on the crosslinked polymer microparticles having the above-described properties.
  • the method of forming the metal coating film consists broadly of 1) a pretreatment process (catalytic process) for bases and 2) an electrolysis plating process.
  • a conventional catalytic process consisting of a sensitization process using SnCl 2 (tin chloride) and an activation process using PdCl 2 (palladium chloride), is carried out.
  • the electroless plating process a given amount of the crosslinked polymer microparticles, subjected to the pretreatment process, are added to a temperature- and pH-controlled plating bath at a concentration of 1-10 g/l, and are thoroughly dispersed therein.
  • a given amount of a dispersing agent may also be added to the plating bath in order to promote the dispersion of the base particles.
  • a dispersing agent one or more selected from among polyethylene glycol (molecular weight of 200-20,000), polyalkylene alkyl ether, polyalkylene alkyl ethyl and polyvinyl pyrrolidone (molecular weight of 500-400,000) may be used.
  • the dispersing agent is added to the plating bath at concentrations of 0.1-10000 ppm, and preferably 1-1000 ppm.
  • an ultrasonic stirrer may also be used for the purpose of facilitating the dispersion of the base particles, and can continue to be used during a plating reaction. Then, the plating reaction is carried out using a dropping method, in which a plating solution, divided into a metal salt solution and a reducing agent, is continuously added to the temperature- and pH-controlled plating bath.
  • the metal salt solution in the plating solution is prepared at a concentration of 1-3 moles from a salt that is generally widely used in electroless plating, for example, nickel chloride, nickel sulfate, copper sulfate, copper acetate, cobalt sulfate, palladium chloride, gold cyanide or gold chloride.
  • the reducing agent solution is prepared at a concentration 1-5 times the concentration of the relative metal salt solution using, for example, sodium hypophosphite (NaH 2 PO 2 ), a borohydride compound or hydrazine.
  • electroless plating is carried out according to the dropping method, in which each of these two solutions is continuously added at a constant flow rate.
  • various compounds that promote electroless plating for example, a pH adjuster, a pH buffer, a complexing agent, a promoter, a stabilizer, etc., may, if necessary, be added according to a conventional method known to those skilled in the art.
  • electroless plating is carried out in the following manner.
  • the initial stage of plating is carried out for 1/100-5/1 (preferably 1/50-1/10) of the total plating time, after the pH of the plating bath is adjusted to a value higher than the normal pH level by 1-3.
  • the initial stage of plating is carried out for 1/100-5/1 (preferably, 1/50-1/10) of the total plating time by simultaneously adding 1/100-1/5 (preferably 1/20-1/5) of the amount of each of metal salt and reducing agent, which is to be added throughout the plating process, and then the plating solution is added according to the dripping method to continue to carry out the plating reaction.
  • the rate of the initial plating reaction is set at a relatively high level in order to solve problems of plating uniformity and reproducibility, which can occur in the dropping method due to the low plating rate at the initial stage of the plating process.
  • the present inventors have found that this agglomeration of plated particles occurs predominantly at the initial stage of plating reaction.
  • the dispersion of plated particles can be improved by placing an intermission of 1/100-1/5 (preferably 1/50-1/10) of the total plating time, in which the addition of the metal salt and the reducing agent is stopped, at the time of completion of the initial plating stage, carrying out more intensive mixing than in the initial plating stage after the intermission period, so as to sufficiently disperse the plated particles, which have been weakly agglomerated in an earlier stage of plating, and then starting to add the plating solution again.
  • the intermission time is excessively short, no improvement in the dispersion of plated particles will be obtained, and if it is excessively long, the plating reaction will stop.
  • the intensive mixing can be performed either by increasing the stirring speed of the stirrer (including a high-speed stirrer) used in the initial plating stage or by increasing stirring force using a high-speed stirrer instead of a general stirrer used in the initial plating stage.
  • the intensity of stirring for the intensive mixing can be experimentally determined in consideration of the size of a plating bath, the size of working volume, the concentration of solids, etc.
  • the above-described electroless plating method can form a single-layer coating film or a multilayer coating film made of more than two materials.
  • an Ni coating film or an Ni-Au double-layer coating film is formed.
  • the Ni coating film can provide an electroless plating layer that has good adhesion to the base resin particles and good peel resistance. Also, it is easy to form an Au layer on the Ni coating film, and the Ni coating layer can ensure a firm bond with a coating layer plated thereon.
  • the formation of the Ni-Au double-layer coating film has an advantage in that it can increase the conductive performance compared to that of a single-layer coating film.
  • the thickness of the coating film formed on the base particles is 10- 500 ran for a single-layer coating film and 10-1000 ran for a double-layer coating film, but the scope of the present invention is not limited thereto.
  • the conductive particles prepared according to the present invention are high-quality, conductive, electroless-plated particles, which have excellent plating uniformity, plating reproducibility and dispersion properties, can be used in the formation of fine interconnections, have no problem of limited electrical capacity in electrical connection, and do not cause a leakage phenomenon.
  • Example 1 After washing, the particles were immersed in an aqueous solution of SnCl 2 (1.0 g/ €) for 3 minutes. Then, the particles were washed with cold deionized water. Then, the particles were immersed in an aqueous solution of PdCl 2 (0.1 g/£) for 3 minutes, and then washed several times with cold deionized water, thus obtaining slurry.
  • SnCl 2 1.0 g/ €
  • PdCl 2 0.1 g/£
  • the metal salt solution and the reducing agent solution were continuously added to the plating bath, until the color of the slurry turned black.
  • the initial stage of plating was performed while the pH was maintained at 6.5.
  • the pH of the plating bath was adjusted to a set value of 5, and an additional plating reaction was carried out, such that the total plating time was 120 minutes.
  • ultrasonic waves of 40 kHz were applied to the plating bath using an ultrasonic dispersion device (BRANSON model 5210).
  • Example 2 In this Example, the slurry prepared in Preparation Example was thoroughly dispersed, as in Example 1.
  • Example 2 in which the initial stage of plating was carried out by adding the plating solution according to the dropping method, 10 ml of each of a metal salt solution (containing 1 mole of nickel sulfate) and a reducing agent solution (containing 2.5 moles of sodium hypophosphite) was added to a plating bath having a temperature of 50 ° C and a pH of 6.5, and thus the plating reaction took place. Then, the color of the slurry immediately turned black, and for 10 minutes after that point in time, the initial stage of plating was performed while the pH was maintained at 6.5. Then, the pH of the plating bath was adjusted to 5 and, at the same time, each of the solutions was added to the plating bath at a rate of 1 iniVmin to carry out an additional plating reaction. The total plating time was 120 minutes.
  • a metal salt solution containing 1 mole of nickel sulfate
  • a reducing agent solution containing 2.5 moles of sodium hypophosphite
  • the obtained nickel-plated particles were washed three times with ion-exchanged water, washed with methanol and then dried in a vacuum, thus obtaining nickel-plated particles.
  • the formed nickel plating layer had a thickness of about 120 ran.
  • a scanning electron microscope photograph of the surface of the obtained plated particles is shown in FIG. 2.
  • Example 3 The process of Example 1 was repeated, except that the initial stage of plating was followed by an intermission of 5 minutes, during which the addition of the plating solution was interrupted, and then the stirring speed of the stirrer was increased by 50% and the plating reaction was carried out.
  • the formed nickel plating layer had a thickness of about
  • Example 4 The process of Example 2 was repeated, except that the initial stage of plating was followed by an intermission of 5 minutes, during which the addition of the plating solution was interrupted, and then the stirring speed of the stirrer was increased by 50% and the plating reaction was carried out.
  • the formed nickel plating layer had a thickness of about
  • Example 5 The process of Example 1 was repeated, except that the initial stage of plating was followed by an intermission of 5 minutes, during which the addition of the plating solution was interrupted, and then the stirrer was replaced with a high-speed stirrer, and the plating reaction was carried out.
  • the obtained nickel-plated particles were washed three times with ion-exchanged water, washed with methanol, and then dried in a vacuum, thus obtaining nickel-plated particles.
  • the formed nickel plating layer had a thickness of about 120 ran.
  • Example 2 The process of Example 2 was repeated, except that the initial stage of plating was followed by an intermission of 5 minutes, during which the addition of the plating solution was interrupted, and then the stirrer was replaced with a high-speed stirrer, and the plating reaction was carried out.
  • the obtained nickel-plated particles were washed three times with ion-exchanged water, washed with methanol, and then dried in a vacuum, thus obtaining nickel-plated particles.
  • the formed nickel plating layer had a thickness of about 120 ran.
  • Example 1 The process of Example 1 was repeated, except that the entire plating process, including the initial stage of plating, was carried out at a pH of 5. After completion of the plating process, the obtained nickel-plated particles were washed three times with ion-exchanged water, washed with methanol, and then dried in a vacuum, thus obtaining nickel-plated particles. The formed nickel plating layer had a thickness of about 110 ran. A scanning electron microscope photograph of the surface of the obtained plated particles is shown in FIG. 5. Comparative Example 2 The process of Example 2 was repeated, except that the amount of each of the solutions added at the initial stage of plating was 2 ml.
  • the formed nickel plating layer had a thickness of about
  • Example 2 The process of Example 2 was repeated, except that the temperature of the plating bath at the initial stage of plating was room temperature.
  • the formed nickel plating layer had a thickness of about
  • SEM scanning electron microscope
  • the dispersion of the plated particles was measured by dispersing 10 g of the plated particles, having plating uniformity observed as described above, in ultrapure water, classifying the particle solution through an electroformed sieve having 5- ⁇ m pores, measuring the amount of particles recovered relative to the amount of particles introduced, and calculating the degree of dispersion according to Math Equation 2 below on the basis of the measurement results.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

L'invention concerne un procédé de dépôt autocatalytique de métal de particules polymères réticulées monodispersées et des particules plaquées préparées à partir de ce procédé. Ce procédé est mis en oeuvre au moyen d'un procédé de déversement, dans lequel une solution de plaquage, divisée en une solution de sel métallique et une solution de sel de réduction, est ajoutée en continu à un bain de plaquage. Dans le procédé de dépôt autocatalytique de métal de particules polymères réticulées monodispersées, l'uniformité du plaquage, la reproductibilité du plaquage et les propriétés de dispersion sont améliorées par ajustement du pH dans la phase initiale de réaction de plaquage, améliorant le procédé d'addition de solution de plaquage, ajoutant un intervalle et sélectionnant un procédé de brassage adéquat.
PCT/KR2007/003683 2007-07-31 2007-07-31 Procédé de dépôt autocatalytique de particules polymères réticulées monodispersées à diamètre micronique et particules plaquées correpondantes WO2009017266A1 (fr)

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PCT/KR2007/003683 WO2009017266A1 (fr) 2007-07-31 2007-07-31 Procédé de dépôt autocatalytique de particules polymères réticulées monodispersées à diamètre micronique et particules plaquées correpondantes

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PCT/KR2007/003683 WO2009017266A1 (fr) 2007-07-31 2007-07-31 Procédé de dépôt autocatalytique de particules polymères réticulées monodispersées à diamètre micronique et particules plaquées correpondantes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2449154A4 (fr) * 2009-06-29 2017-01-04 Auckland UniServices Limited Procédé de placage ou de revêtement pour produire un revêtement métal-céramique sur un substrat

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118866A (ja) * 1993-10-21 1995-05-09 Nippon Chem Ind Co Ltd 分散性に優れた球状無電解めっき粉末、導電性材料およびその製造方法
US6770369B1 (en) * 1999-02-22 2004-08-03 Nippon Chemical Industrial Co., Ltd. Conductive electrolessly plated powder, its producing method, and conductive material containing the plated powder
KR20070055511A (ko) * 2004-08-18 2007-05-30 후지필름 가부시키가이샤 표면기능성 부재의 제조방법, 및, 도전막의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118866A (ja) * 1993-10-21 1995-05-09 Nippon Chem Ind Co Ltd 分散性に優れた球状無電解めっき粉末、導電性材料およびその製造方法
US6770369B1 (en) * 1999-02-22 2004-08-03 Nippon Chemical Industrial Co., Ltd. Conductive electrolessly plated powder, its producing method, and conductive material containing the plated powder
KR20070055511A (ko) * 2004-08-18 2007-05-30 후지필름 가부시키가이샤 표면기능성 부재의 제조방법, 및, 도전막의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2449154A4 (fr) * 2009-06-29 2017-01-04 Auckland UniServices Limited Procédé de placage ou de revêtement pour produire un revêtement métal-céramique sur un substrat
US9562302B2 (en) 2009-06-29 2017-02-07 Auckland Uniservices Limited Plating or coating method for producing metal-ceramic coating on a substrate

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