JP6058728B2 - Electrolytic plating electrode and electrolytic plating apparatus including the same - Google Patents

Description

  The present invention relates to an electrode for electroplating and an electroplating apparatus including the electrode, and more specifically, an electrode for electroplating in which a nonconductive pattern is partially formed on the surface of a conductive material and electrolysis including the electrode. The present invention relates to a plating apparatus.

  The present invention relates to an electrode for electroplating and an electroplating apparatus including the electrode, and the electrode and the apparatus including the electrode are coated with a different metal on the surface of the metal powder and finally have a core-shell structure. Is used to synthesize metal composites having

  The metal composite having the core-shell structure or the metal powder material formed of the metal composite is not only a conductive paste used in electronic packaging, solar cells, mobile electronic devices, etc., but also from electronic devices. The present invention can be applied to various fields such as an electromagnetic wave shielding paste for shielding generated electromagnetic waves.

  Currently, in the technical field to which the present invention belongs, technical development for improving not only the price competitiveness of metal composites but also the reliability, quality and stability of metal composites is continuously required.

  Generally, methods for synthesizing a metal composite having a core-shell structure include electroless plating or galvanic displacement reaction.

  Electroless plating is a term that means displacement plating, contact plating, non-catalytic chemical plating, or catalytic chemical plating, but usually does not receive electric energy and reduces metal ions in an aqueous metal salt solution to a reducing agent. It means catalytic chemical plating in which metal is deposited on the surface of the object to be plated by reducing it in an autocatalytic manner by force. The manufacture of the core-shell composite by the electroless plating has a problem that the reaction conditions have to be difficult for different metals to form the core part and the shell part, and various reducing agents and complexing agents. Etc. must be used, and there is a problem in wastewater treatment and costs.

  The galvanic substitution reaction is a spontaneous reaction that occurs due to a potential difference between two metals, and this potential difference occurs when a potential difference occurs between the metal to be plated and the dissimilar metal that exists in an ionic state in the solution. Due to the potential difference, the metal to be plated is dissolved in the solution in an ionic state, and the dissimilar metal existing in the solution in the ionic state is coated on the surface of the metal to be plated by being reduced. is there.

  The electroless plating and the galvanic replacement reaction are mutually competitive reactions that can occur simultaneously under the same conditions. Therefore, when the thickness of the shell portion corresponding to the coating layer of the metal powder is increased, or when appropriate reaction conditions cannot be found within the reaction scale, there is a high possibility that pores are generated inside the composite. There are disadvantages (Fig. 1). As shown in FIG. 2, when a composite having a core-shell structure in which voids are present is used as an electronic material, defects such as blisters, reduced conductivity, and solvent absorption may occur.

  Electrolytic plating has been proposed to solve the problems of electroless plating and galvanic substitution reaction as described above. Usually, when using an electroplating apparatus, a plurality of metal powders are not individually coated. In addition, a plurality of metal powders are agglomerated by being simultaneously coated with a high probability.

  Instead of having a single core part, the aggregate thus aggregated has two or more multiple core parts like peanuts, but voids are formed inside the aggregated complex. There is a high possibility that this may be accompanied by defects such as blistering, reduced conductivity and solvent absorption.

  As the prior art, there are Patent Document 1 and Patent Document 2, but each of the above-mentioned documents merely discloses a general plating processing method and a plating processing apparatus using the same. It does not introduce an innovative way to solve this problem.

Korean Published Patent Publication No. 1998-079372 Korean Published Patent Publication No. 2004-0072704

  The present inventors have long developed a plating method and a plating electrode for improving the reliability, quality, and stability of a core-shell structure metal composite produced through various known methods. As a result, the inventors have developed a plating method that can improve the reliability, quality, and stability of a metal composite having a core-shell structure, and a plating electrode that can be used in the plating method.

  An object of the present invention is to provide a plating electrode for use in a plating method capable of improving the reliability, quality, stability and the like of a metal composite having a core-shell structure.

  Another object of the present invention is to provide a plating apparatus including a plating electrode capable of improving the reliability, quality, stability and the like of a metal composite having a core-shell structure.

In order to solve the above technical problem,
According to an aspect of the present invention, an exposed surface of the conductive material including a non-conductive pattern partially formed on the surface of the conductive material, the non-conductive pattern being formed, and an object to be plated. The electrode for electroplating which performs the surface plating of the said to-be-plated object can be provided by contacting.

  In one embodiment, a plurality of objects to be plated may not be in contact with the exposed surface of the conductive material on which the nonconductive pattern is not formed.

  In one embodiment, the mesh size of the exposed surface of the conductive material on which the nonconductive pattern is not formed may be 0.5 to 2 times the diameter of the object to be plated.

In one embodiment, the conductive material may be an electrically conductive metal.
In one embodiment, the electrically conductive metal may be at least one selected from Ag, Au, Al, Ni, Cu and Pt.
In one embodiment, the conductive material may have at least one shape selected from a sheet, a wire, a disk, a rod, and a foil.
In one embodiment, the non-conductive pattern may have at least one shape selected from a mesh, a striped pattern, a spiral shape, and a spherical shape.
In one embodiment, the non-conductive pattern may be a positive pattern.

  In one embodiment, the non-conductive pattern includes non-conductive metal oxide, methyl pentene polymer, polyamide, polytetrafluoroethylene, polyethylene, polypropylene, polyisopyrene, polyurethane, polycarbonate, polyimide, polystyrene, polysulfone, polyvinyl chloride and polyvinyl chloride. It may be formed by coating with at least one substance selected from indene chloride.

  In one embodiment, the ratio of the total area of the non-conductive region where the non-conductive pattern is formed to the total area of the conductive region where the non-conductive pattern is not formed on the surface of the conductive material. 20: 80-95: 5 may be sufficient.

In one embodiment, a non-conductive pattern may be formed by filling a non-conductive material in an inscribed region of the conductive material provided with an inscribed region on a surface.
In one embodiment, the object to be plated may be a metal powder.

According to another aspect of the present invention, there is provided an electroplating apparatus comprising: a reaction tank; the electroplating electrode disposed in the reaction tank; and a power supply unit for applying a voltage to the electroplating electrode. Can do.
In one embodiment, the reaction vessel may further include a stirring unit.
In one embodiment, the reaction vessel may be a cylindrical barrel, and the electrode for electrolytic plating may be disposed along an inner peripheral surface of the reaction vessel of the cylindrical barrel.

  According to one embodiment of the present invention, the contact area between the surface of the object to be plated and the electrode can be minimized by using an electrode for electrolytic plating in which a non-conductive pattern is partially formed. Through this, it is possible to suppress the formation of a metal composite having a multi-core portion that is generated by simultaneously contacting and coating a plurality of objects to be plated on a conductive region where a nonconductive pattern is not formed.

  In addition, according to an embodiment of the present invention, since the surface to be plated can be coated with a different metal before galvanic corrosion occurs, the reliability, quality and stability of the generated metal composite of the core-shell structure can be obtained. Etc. can be improved.

  Furthermore, according to an embodiment of the present invention, various types of different metals can be coated on the surface of the object to be plated without being specified as the object to be plated.

It is the figure which showed the process in which a space | gap is formed inside the metal composite of a core-shell structure manufactured by the electroless plating or the galvanic substitution reaction. It is a SEM photograph of a core-shell structured metal composite produced by electroless plating or galvanic substitution reaction. It is the figure which showed the electrode for electroplating in which the nonelectroconductive pattern was partially formed on the surface of the conductive substance which concerns on one Example of this invention. It is the figure which showed the electrode for electroplating in which the nonelectroconductive pattern was partially formed on the surface of the conductive substance which concerns on one Example of this invention. It is sectional drawing of the electrode for electroplating which concerns on one Example of this invention. It is sectional drawing of the electrode for electroplating which concerns on one Example of this invention. It is sectional drawing of the electrode for electroplating which concerns on one Example of this invention. It is sectional drawing of the electrode for electroplating which concerns on one Example of this invention. It is the figure which showed the electroplating apparatus which concerns on one Example of this invention.

  For convenience, certain terms are defined herein for convenience in understanding the invention. Unless defined otherwise in this application, scientific and technical terms used in the present invention will have the meanings that are commonly understood by those of ordinary skill in the relevant art. Also, unless otherwise specified in context, it should be understood that terms in the singular form also include the plural form and terms in the plural form also include the singular form.

  Hereinafter, an electrode for electroplating and an electroplating apparatus including the same according to an embodiment of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified in various forms, and the scope of the present invention is not limited by the following description.

  According to an aspect of the present invention, an exposed surface of the conductive material including a non-conductive pattern partially formed on the surface of the conductive material, the non-conductive pattern being formed, and an object to be plated. The electrode for electroplating which performs the surface plating of the said to-be-plated object can be provided by contacting.

  In one embodiment, a plurality of objects to be plated may not be in contact with the exposed surface of the conductive material on which the nonconductive pattern is not formed. When the object to be plated is in direct contact with the conductive region, a coating layer, which is a shell portion, is formed on the surface of the object to be plated by reduction of ions of dissimilar metals contained in the plating solution.

  At this time, a non-conductive pattern is partially formed on the surface of the conductive material, and the non-conductive pattern is not formed, that is, the conductive material not blocked by the non-conductive pattern. The surface may be exposed in the form of a mesh (mesh or opening). In addition, it is not always necessary to form a net-like surface of the conductive material that is not blocked by the non-conductive pattern.

  As described throughout this application, a mesh is a region where the non-conductive pattern is not formed on the surface of the conductive material; a region not obstructed by the non-conductive pattern; and between the non-conductive patterns. The surface of the conductive material exposed to the surface; or the conductive region may be variously expressed, but both may be used in the same meaning. This can be more clearly understood through the attached drawings.

  A coating layer may be formed on the surface of the object to be plated by contacting the surface to be plated with the surface of the conductive material that is not blocked by the nonconductive pattern.

  Here, the size of the mesh is limited so that a plurality of objects to be plated are not in contact with the surface of the conductive material exposed in the mesh form at the same time, but the objects to be plated are in contact with each other individually.

  That is, when a plurality of objects to be plated are in contact with a conductive region at the same time, a plurality of objects to be plated are simultaneously coated to induce agglomeration of the composite, and eventually, a metal composite having multiple core parts. Can be generated. Since the metal composite having such a multi-core portion must be irregular in structure and shape, a metal composite having uniform physical properties cannot be obtained. The excellent reliability, quality and stability cannot be ensured.

  Accordingly, an object of the present invention is to minimize the contact area between the surface to be plated and the electrode made of the conductive material by using an electrode for electrolytic plating in which a non-conductive pattern is partially formed. This is achieved by adjusting the size of the non-conductive pattern in order to prevent a plurality of objects to be plated from simultaneously contacting the exposed surface of the conductive material on which the non-conductive pattern is not formed. can do.

  Eventually, the size of the non-conductive pattern can be adjusted to determine the preferred size of the conductive region that is the exposed surface of the conductive material where the non-conductive pattern is not formed. Through this, it is possible to induce a single plating target to be contacted and coated on a conductive region where a non-conductive pattern is not formed, so that a plurality of plating targets are simultaneously contacted and coated. Generation of a metal composite having a multiple core part can be suppressed.

  As described above, a non-conductive pattern is partially formed on the surface of the conductive material, and the surface of the conductive material not blocked by the non-conductive pattern is exposed in the form of a network. May be.

  In one embodiment, the mesh size of the exposed surface of the conductive material on which the nonconductive pattern is not formed may be 0.5 to 2 times the diameter of the object to be plated.

  In the embodiment of the present invention, the size of the object to be plated (core part) used for forming the core-shell composite is preferably in micro units, but is not necessarily limited thereto. Therefore, a conductive region, that is, a mesh size (mesh size or opening size) that is an exposed surface of the conductive material on which the non-conductive pattern is not formed is also a micro unit. However, it is not necessarily limited to this, and is 0.5 to 2 times the diameter of the object to be plated used, and more preferably 0.5 to 1.5 times.

  That is, depending on the size of the object to be plated used to form the core-shell composite, the size of the nonconductive pattern and / or the exposed surface of the conductive material on which the nonconductive pattern is not formed The mesh size of a certain conductive region can vary, but the size should be such that only one object to be plated can be contacted and coated on the conductive region where the non-conductive pattern is not formed. preferable.

  In one embodiment, the conductive material may be at least one selected from electrically conductive metals such as Ag, Au, Al, Ni, Cu, and Pt, and may be a sheet, a wire, a disk, a rod, and a foil. It may have at least one shape selected from, but is not necessarily limited thereto.

  Therefore, the type and shape of the conductive material can be freely adjusted and changed according to the usage and conditions of the electrode for electroplating according to one embodiment of the present invention, so it is not specified as an object to be plated, There is an advantage that various kinds of different metals can be coated on the surface of the object to be plated.

  Here, the type and shape of the substance to be plated can be freely adjusted and changed according to the intended use and conditions of the electrode for electrolytic plating according to an embodiment of the present invention. In particular, the shape of the object to be plated can be selected from powder, sheet, wire, disk, rod and foil, but is preferably in the form of a spherical powder.

  In general, an electrode for electroplating is disposed in a reaction tank of an electroplating apparatus, and a voltage having a certain size is applied to the electrode by a power supply unit, and a constant current is applied to the electrode by applying the voltage. It begins to flow.

  However, the present invention is characterized in that a non-conductive pattern, that is, an insulating pattern is partially formed on the surface of the conductive material, so that a voltage having a certain size is generated by the power supply unit. The current that is applied to the conductive material and flows may be limitedly provided to an object to be plated that is in contact with the exposed surface of the conductive material where the nonconductive pattern is not formed, that is, the conductive region.

  In one embodiment, the nonconductive pattern may have at least one shape selected from a mesh, a striped pattern, a spiral shape, and a spherical shape, but the nonconductive pattern is also used for an electrode for electroplating. It can be freely adjusted and changed according to the conditions. The nonconductive pattern may be a nonconductive material and / or an insulating material, such as a nonconductive metal oxide, methylpentene polymer, polyamide, polytetrafluoroethylene, polyethylene, polypropylene, polyisopyrene, polyurethane, polycarbonate, polyimide. , Polystyrene, polysulfone, polyvinyl chloride, and polyvinyl indene chloride may be formed by coating with at least one substance.

  Referring to FIG. 3 illustrating an electrode for electroplating in which a non-conductive pattern is partially formed on the surface of a conductive material according to an embodiment of the present invention, the electrode for plating is a wire-shaped conductive material. The surface of the material 301 is coated with a non-conductive pattern 302, so that the exposed surface of the conductive material without the non-conductive pattern, that is, the conductive region 303 may be formed in a spherical shape.

  Referring to FIG. 4, the plating electrode has a non-conductive pattern 403 coated on a surface of a wire-shaped conductive material 401 in a mesh form, thereby forming a non-conductive pattern. The non-conductive region 402 may be formed in a square shape.

  Here, the conductive region generally has a concept that is distinguished from a “conductive hole” provided in an electrode for electrolytic plating for smooth communication of a plating solution, and plating is performed through the conductive region. It means an exposed surface of the conductive material in which the liquid does not pass but the non-conductive pattern is not formed.

  That is, the surface of the object to be plated is placed in the plating solution by directly contacting the conductive region that is the exposed surface of the conductive material on which the nonconductive pattern is not formed. The shell part is formed by the reduction of the ions of the contained different metals.

  For example, when the object to be plated is a metal powder, a shell is formed on the surface of the metal powder by reduction of different metal ions contained in the plating solution. The body can be formed.

  Also, a conductive region where the nonconductive pattern is not formed on the surface of the conductive material, more specifically, the mesh size of the portion 303 or 402 of the conductive material exposed between the nonconductive patterns. Is determined by the size of the object to be plated, and is preferably of a size that can prevent a plurality of objects to be plated from simultaneously contacting one mesh. Therefore, the mesh size is preferably 0.5 to 2 times the diameter of the metal powder to be plated. For example, when the diameter of the metal powder to be plated is 20 μm, the mesh size of a part of the conductive material exposed between the nonconductive patterns is 10 μm to 40 μm, and is 10 μm to 30 μm. It is preferable.

  The present invention is characterized in that a non-conductive pattern, that is, an insulating pattern is partially formed on the surface of the conductive material, so that a voltage having a certain size is transmitted by the power supply unit. The current flowing when applied to the conductive material can be limitedly supplied to the object to be plated, preferably a metal powder in a micro unit, in contact with the conductive region where the non-conductive pattern is not formed.

  That is, according to the present invention, by partially forming a non-conductive pattern on the surface of the conductive material, contact between the conductive region and the metal powder of the micro unit can be minimized, Thereby, the production | generation of the multi-core metal complex produced | generated by coating a several metal powder simultaneously can be suppressed.

  In one embodiment, the ratio of the total area of the non-conductive region where the non-conductive pattern is formed on the surface of the conductive material to the total area of the conductive region where the non-conductive pattern is not formed is 20: 80-95: 5 may be sufficient.

  The present invention aims to minimize contact between the conductive region and the micro-unit metal powder by partially forming a non-conductive pattern on the surface of the conductive material. If the ratio of the conductive region is less than 5%, the coating efficiency on the surface of the object to be plated is drastically reduced, which is not suitable for manufacturing a core-shell composite. On the other hand, if the ratio of the conductive region exceeds 80%, the probability that a plurality of metal powders are coated at the same time increases, so the meaning of partially forming a non-conductive pattern on the conductive material is insignificant. It can only be a thing.

  As described above, a non-conductive pattern is partially formed on the surface of the conductive material, and the non-conductive pattern is not formed, i.e., is not blocked by the non-conductive pattern. The surface of the sex substance may be exposed in the form of a kind of mesh.

  Referring to FIG. 5, which is a cross-sectional view of an electrode for electroplating according to an embodiment of the present invention, a non-conductive pattern 501 partially formed on the surface of the conductive material 502 may be a positive pattern. Good. A conductive material is exposed at the lower part of the inscribed region formed by the positive non-conductive pattern 501, and the exposed conductive material and the object to be plated come into contact with each other.

  In FIG. 5, the exposed surface of the conductive material 502 that is not obstructed by the nonconductive pattern is shown as a plane, but it may be formed on a convex or concave surface.

  Referring to FIG. 6, which is a cross-sectional view of an electrode for electrolytic plating according to another embodiment of the present invention, a non-conductive pattern 601 partially formed on the surface of the conductive material 602 is an embossed pattern. Also good. A conductive material is exposed at a lower portion of an inscribed region formed by the positive non-conductive pattern 601, and the exposed conductive material comes into contact with the object to be plated.

  However, the electroplating electrode according to FIG. 6 differs from the electroplating electrode according to FIG. 5 in that the conductive material 602 itself has an inscribed region on the surface, and the inlaid region is filled with a nonconductive material. The non-conductive pattern 601 may be formed higher than the region where the conductive material 602 is etched.

  In FIG. 6, the exposed surface of the conductive material 602 that is not blocked by the nonconductive pattern may be formed as a convex or concave surface as well as a flat surface.

  Referring to FIG. 7, which is a cross-sectional view of an electrode for electrolytic plating according to still another embodiment of the present invention, a nonconductive material is filled in an inscribed region of the conductive material 702 having an inscribed region on the surface. The non-conductive pattern 701 may be formed to have the same height as a part of the conductive material or the height of the embossed region 703, so that the embossed region 703 of the conductive material is exposed to the outside. It comes in contact with the object to be plated. Here, a part of the conductive material or the embossed region 703 may be formed on a concave surface.

  Referring to FIG. 8, which is a cross-sectional view of an electrode for electrolytic plating according to still another embodiment of the present invention, a nonconductive material is filled in the inscribed region of the conductive material 802 provided with an inscribed region on the surface. The non-conductive pattern 801 may be formed to have the same height as a part of the conductive material or the height of the embossed region 803, so that the embossed region 803 of the conductive material is exposed to the outside. It comes in contact with the object to be plated. However, unlike FIG. 7, a part of the conductive material or the embossed region 803 may be formed on a convex surface.

  According to another aspect of the present invention, there is provided an electrolytic plating apparatus including: a reaction tank 901; an electrode for electrolytic plating 902 disposed in the reaction tank; and a power supply unit for applying a voltage to the electrode for electrolytic plating. be able to. Here, the electrode for electroplating 902 is characterized in that only a part 903 of the conductive material is exposed by forming a non-conductive pattern partially on the surface of the conductive material.

  Referring to FIG. 9 illustrating an electroplating apparatus according to an embodiment of the present invention, the reaction vessel 901 may further include a stirring unit 904. The stirring unit 904 is provided as a means for mixing the object to be plated and the plating solution.

  In one embodiment, the reaction vessel 901 may be a cylindrical barrel, but is not necessarily limited thereto, and is suitable for configuring an electroplating apparatus, for example, having a shape such as a spherical shape. May be.

  In one embodiment, the electrode for electrolytic plating may be disposed along the inner peripheral surface of the reaction vessel of the cylindrical barrel. In another embodiment, the stirring part 904 may further include the electrode for electrolytic plating. Therefore, the stirring unit can be provided not only as a means for mixing the object to be plated and the plating solution, but also as an electrode for electrolytic plating.

  In the above, one embodiment of the present invention has been described. However, a person who has ordinary knowledge in the corresponding technical field may recognize the constituent elements within the scope of the present invention described in the claims. It can be said that various modifications and changes can be made to the present invention by additions, changes, deletions, additions, and the like, and these are also included within the scope of the present invention.

301: Conductive substance 302: Non-conductive pattern 303: Conductive region

Claims (9)

Non-conductive metal oxide, methylpentene polymer, polyamide, polytetrafluoroethylene, polyethylene, partially formed on the surface of the conductive metal selected from Ag, Au, Al, Ni, Cu and Pt . Including a non- electrically conductive pattern formed by coating with at least one material selected from polypropylene, polyisoprene, polyurethane, polycarbonate, polyimide, polystyrene, polysulfone, polyvinyl chloride and polyvinyl inden chloride ;
An electrode for electrolytic plating that performs surface plating of the object to be plated by contacting the exposed surface of the electrically conductive metal and the object to be plated, in which the non- electrically conductive pattern is not formed ,
A plurality of objects to be plated do not simultaneously contact the exposed surface of the electrically conductive metal where the non-electrically conductive pattern is not formed,
The exposed surface of the electrically conductive metal in which the non-electrically conductive pattern is not formed is exposed in a mesh form, and the mesh size is 0.5 to 2 times the diameter of the object to be plated.
Electrode for electroplating. The electrode for electrolytic plating according to claim 1, wherein the electrically conductive metal has at least one shape selected from a sheet, a wire, a disk, a rod, and a foil. The electrode for electroplating according to claim 1, wherein the non- electrically conductive pattern has at least one shape selected from a mesh, a striped pattern, a spiral shape, and a spherical shape. The electrode for electroplating according to claim 1, wherein the non- electrically conductive pattern is a positive pattern. On the surface of the electrically conductive metal ,
The ratio of the total area of the electrically conductive region in which the total area electrically nonconductive pattern is not formed of non-electrically conductive pattern electrically nonconductive region formed of 20: 80 to 95: A 5 The electrode for electrolytic plating according to claim 1. The electrode for electrolytic plating according to claim 1 , which is used for plating metal powder . Reaction tank;
The electrode for electrolytic plating according to any one of claims 1 to 6 disposed in the reaction vessel; and a power supply unit for applying a voltage to the electrode for electrolytic plating;
Electrolytic plating apparatus including The electroplating apparatus according to claim 7 , wherein the reaction vessel further includes a stirring unit. The reaction vessel is a cylindrical barrel;
The electroplating apparatus according to claim 7 , wherein the electrode for electroplating is disposed along an inner peripheral surface of a reaction tank of the cylindrical barrel.