Plated medium, method for producing plated medium, and method for reusing plated medium

Abstract

One embodiment of the present invention provides a plating medium comprising: a core; and a shell provided on the surface of the core. The shell constitutes a multilayer body of two or more metal-containing layers.

Description

Plating media, method for making plating media, and method for reusing plating media

[0001] The present invention relates to plating media, a method for making plating media, and a method for reusing plating media.

[0002] Plating apparatuses using barrel plating have been known for some time. These plating apparatuses include a barrel, an anode electrode, and a cathode electrode in a plating bath containing a plating solution. The barrel is rotatable about its axis, and a workpiece to be plated, conductive plating media, and the cathode electrode are positioned inside the barrel. The conductive plating media can be used to efficiently pass current through the workpiece to improve plating efficiency.

[0003] In this configuration, when a current is applied between the anode electrode and the cathode electrode, a plating film can be formed on the surface of the object to be plated and the media through the plating solution from the plating film supply source of the anode electrode.

[0004] JP 2010-100920 A

[0005] In plating equipment, it is desirable to reuse plating media from the viewpoint of efficient use, and it is also desirable to provide plating media with more suitable electrical conductivity and / or other properties besides electrical conductivity, such as electrical conductivity and corrosion resistance.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide plating media that can be reused and that can provide more suitable electrical conductivity and / or properties other than electrical conductivity, such as electrical conductivity and corrosion resistance, a method for producing the plating media, and a method for reusing the plating media.

[0007] In order to achieve the above object, one embodiment of the present invention provides a plating medium comprising a core and a shell provided on the surface of the core, wherein the shell constitutes a multi-layer body of two or more metal-containing layers.

[0008] In order to achieve the above object, one embodiment of the present invention provides a method for preparing plating media, which includes the steps of preparing a core and forming a shell having a multilayer structure of two or more metal-containing layers on the surface of the core.

[0009] In order to achieve the above object, one embodiment of the present invention provides a method for recycling plating media, which comprises a core and a shell provided on the surface of the core, the shell constituting a multi-layer body of two or more metal-containing layers, and which comprises peeling off the object to be plated located on the surface of the plating media and at least one metal-containing layer of the plating media after plating.

[0010] According to one embodiment of the present invention, it is possible to reuse plating media and provide better conductivity and / or other properties besides conductivity, such as conductivity and corrosion resistance.

[0011] FIG. 1 is a cross-sectional view schematically showing a plating apparatus (before energization) equipped with plating media according to one embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing plating media according to a first embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing plating media according to a second embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing plating media according to a third embodiment of the present invention. FIG. 5 is a cross-sectional view schematically showing a state in which a plating layer has been formed on the surface of plating media according to the first embodiment of the present invention. FIG. 6 is a cross-sectional view schematically showing a process for producing plating media according to the first embodiment of the present invention. FIG. 7 is a cross-sectional view schematically showing a process for producing plating media according to a second embodiment of the present invention. FIG. 8 is a cross-sectional view schematically showing a process for producing plating media according to a third embodiment of the present invention. FIG. 9 is a cross-sectional view schematically showing an apparatus used to carry out a method for recycling plating media according to one embodiment of the present invention.

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Although the embodiments may be shown separately for convenience, partial substitution or combination of the configurations shown in different embodiments is possible. Therefore, the present disclosure is not expressly limited to preferred aspects (alone or in combination with other features) that illustrate non-limiting combinations of possible features. In the embodiments described below, descriptions of matters common to the above will be omitted, and only differences will be described. In particular, similar effects due to similar configurations will not be mentioned in each embodiment.

[0013] Among the components in the following embodiments, those not recited in the independent claims are described as optional components. The sizes and size ratios of the components shown in the drawings are not necessarily strict. In each drawing, the same reference numerals are used for substantially the same components, and duplicate descriptions may be omitted or simplified.

[0014] FIG. 1 is a cross-sectional view showing a plating apparatus equipped with plating media according to one embodiment of the present invention.

[0015] 1, a plating apparatus 50 includes a barrel 3, a cathode electrode 4, an anode electrode 5, and a power supply 7 electrically connecting the electrodes in a plating bath 2 containing a plating solution 1. The barrel 3 has the form of a container that can rotate about its axis, and a workpiece 6 to be plated, a conductive medium 10, and the cathode electrode 4 are positioned therein.

[0016] The conductive media 10 can be provided to efficiently pass current through the object 6 to be plated, thereby improving plating efficiency. The cathode electrode 4 can be made of, for example, stainless steel, copper, or the like. The object 6 to be plated can be an electronic component having an electrode. The anode electrode 5 can have a constituent material of a plating layer to be formed on the object 6 to be plated, for example, on the electrode of the electronic component.

[0017] In use, the barrel 3 is rotated about its axis, and the object to be plated housed in the barrel 3 is agitated together with the media 10 in the plating solution 1. Then, the power source 7 is driven to apply a positive voltage to the anode electrode 5 and a negative voltage to the cathode electrode 4, causing a current to flow between the anode electrode 5 and the cathode electrode 4 through the plating solution 1. This allows electrical conduction between the object to be plated 6 and the cathode electrode 4 via the media 10.

[0018] In this current-carrying state, metal ions that can form a plating film and that have dissolved in the plating solution 1 from the anode electrode 5 are reduced on the surface of the object 6 to be plated, forming a metal plating layer on the surface of the object 6. At this time, a metal plating layer can be formed not only on the object 6 to be plated but also on the surface of the media 10.

[0019] First Embodiment The features of the present invention are described below. The present invention is characterized by the configuration of the conductive plating media 10 used in the plating apparatus 50.

[0020] The present inventors have conducted extensive research into the configuration of media 10 that can be reused from the viewpoint of efficient use, and that can provide more suitable conductivity and / or properties other than conductivity, such as conductivity and corrosion resistance, and as a result, have devised a new media 10 having the following configuration.

[0021] FIG. 2 is a cross-sectional view schematically showing a plating medium according to a first embodiment of the present invention.

[0022] As shown in FIG. 2 , the plating media 10 according to the first embodiment includes a core 11 and a shell 12 disposed on the surface of the core 11. In this specification, the core 11 may also be referred to as a core material. The media 10 according to the first embodiment is characterized in that the shell 12 constitutes a multi-layer structure 13 of two metal-containing layers. In the configuration shown in FIG. 2 , the multi-layer structure 13 of the shell 12 includes a first metal-containing layer 14 in contact with the core 11 and a second metal-containing layer 15 located outside the first metal-containing layer 14. As used herein, the term "plating media" refers to an auxiliary medium for facilitating plating processing in a plating apparatus, and may also be referred to as a plating auxiliary member, plating media, plating catalyst, plating media, plating tool, or plating jig.

[0023] Although not particularly limited, the core 11 may be made of at least one material selected from the group consisting of ceramic, resin, and glass. The ceramic may include at least one material selected from the group consisting of alumina, zirconia, sapphire, yttria, magnetite, cermet, silicon carbide, silicon nitride, aluminum nitride, steatite, cordierite, and quartz glass. The resin may include at least one material selected from the group consisting of PP, PE, and PTFE.

[0024] Although not particularly limited, the first metal-containing layer 14 may contain, as a main component, at least one element selected from the group consisting of Ni, Cu, Pd, Sn, Ag, Zn, Co, Au, Pt, In, and Bi. The second metal-containing layer 15 may contain at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt, and Au. For example, Ni applied by electroless plating (a Ni layer or scattered Ni) may constitute the first metal-containing layer 14, and a Ni layer applied by electrolytic plating may constitute the second metal-containing layer 15. The first metal-containing layer 14 may also contain additives such as Sn, S, Ni, Co, Fe, C, P, and / or B. As used herein, the term "metal-containing layer" such as the first metal-containing layer may refer not only to a continuous layered structure, but also to a structure in which the metal is discontinuously scattered or dispersed (for example, a structure in which the components of the first metal-containing layer are scattered or dispersed on the surface of core 11, etc.).

[0025] When the metal-containing layer contains Ni as the metal element, corrosion resistance and solder barrier properties are improved. When the metal-containing layer contains Cu as the metal element, electrical conductivity is improved. When the metal-containing layer contains Sn as the metal element, oxidation resistance and anti-seizure properties are improved. When the metal-containing layer contains Pd as the metal element, corrosion resistance and wear resistance are improved. When the metal-containing layer contains Pt as the metal element, corrosion resistance and oxidation resistance are improved. When the metal-containing layer contains Au as the metal element, corrosion resistance, oxidation resistance, electrical conductivity, and low resistance are improved. The properties of these metal elements are the same in the second and third embodiments described below.

[0026] The first metal-containing layer 14 containing the above-mentioned metal elements may be a dry-plated layer or a wet-plated layer. The dry-plated layer can be formed on the surface of the prepared core 11 (corresponding to the core material) using at least one method selected from the group consisting of CVD, sputtering, PVD, vacuum deposition, hot-dip plating, thermal spraying, and lightening (see FIG. 6 ). The first metal-containing layer 14 can also be formed using methods other than plating, such as painting, sol-gel, electrolytic polymerization, and / or electroforming.

[0027] When the first metal-containing layer 14 is a wet-plated layer, it can be formed by performing an electroless plating (or electrolytic plating) process on the surface of the prepared core 11 (corresponding to the core material) (see FIG. 6 ). The electroless plating process requires the application of a catalyst to the surface of the core 11, and the catalyst may contain at least one catalyst selected from the group consisting of Pd, Ag, and Ni. After the first metal-containing layer 14 is formed, the catalyst may remain in the first metal-containing layer 14 or may disappear from the first metal-containing layer 14.

[0028] The catalyst can be applied to the surface of the core 11 by at least one method selected from the group consisting of, for example, a catalyst method, a substitution method, a sensitizing / activating method, and an alkali reduction method (DMAB method). From the viewpoint of suitably applying the catalyst, it is preferable to carry out a degreasing step before applying the catalyst.

[0029] The second metal-containing layer 15 containing the above-described metal elements may be a dry-plated layer or a wet-plated layer. The dry-plated layer can be formed on the surface of the first metal-containing layer 14 by at least one method selected from the group consisting of CVD, sputtering, PVD, vacuum deposition, hot-dip plating, thermal spraying, and lightening (see FIG. 6 ). The second metal-containing layer 15 can also be formed by methods other than plating, such as painting, sol-gel, electrolytic polymerization, and / or electroforming.

[0030] Furthermore, when the second metal-containing layer 15 is a wet-plated layer, it can be formed by performing electroless plating or electrolytic plating on the surface of the formed first metal-containing layer 14 (see FIG. 6 ). In the case of electroless plating, a catalyst may be applied to the surface of the first metal-containing layer 14, and the catalyst may include at least one catalyst selected from the group consisting of Pd, Ag, and Ni. In terms of both production efficiency and cost efficiency, electrolytic plating, which can form a plating layer without using a catalyst, is preferred.

[0031] As described above, in this embodiment, the presence of a multilayer structure having two metal-containing layers allows each metal-containing layer to have the same or different properties, thereby making it possible to provide more suitable electrical conductivity and / or properties other than electrical conductivity.

[0032] 2, for example, both the first metal-containing layer 14 and the second metal-containing layer 15 can have conductive properties, which can more effectively promote electrical connection between the object to be plated 6 and the cathode electrode 4. In other words, the overall electrical conductivity can be further improved.

[0033] Furthermore, first metal-containing layer 14 may primarily have conductive properties, while second metal-containing layer 15, which is the outermost layer, may have other properties in addition to conductivity, such as oxidation resistance. In other words, medium 10 itself may have the property of preventing oxidation.

[0034] This can be effective when storing the media 10 for a long period of time before plating the object to be plated, i.e., before loading the plating media 10 into the barrel of a plating machine. On the other hand, if the media 10 will not be stored for a long period of time, the second metal-containing layer 15 located at the outermost layer does not necessarily need to be oxidation-resistant.

[0035] Furthermore, after the metal plating layer 20 is formed not only on the surface of the object 6 to be plated but also on the surface of the media 10 (see FIGS. 5 and 6 ), the media 10 can be reused by peeling off the metal plating layer 20 and peeling off at least one metal-containing layer that constitutes the shell 12 of the media 10. In FIG. 5 , the media without the metal plating layer 20 is indicated by the reference numeral 10, and the media 10 with the metal plating layer 20 is indicated by the reference numeral 30.

[0036] In one example, as shown in FIG. 6 , the metal plating layer 20 may be stripped and the two metal-containing layers 14, 15 that make up the shell of the media 10 may be stripped. This allows the core 11 (corresponding to the core material) of the media 10 to be reused after stripping. In this case, the surface roughness of the core may be 0.001 μm to 100 μm. Preferably, it is 0.01 μm to 10 μm, more preferably 0.3 μm to 1.1 μm, and even more preferably 0.4 μm to 0.9 μm. The stripped metal-containing layer may also be reused. The components of the metal-containing layer dissolved by the method described below may be recovered as metal by electrodeposition or separated and extracted using an ion exchange column for reuse.

[0037] In this case, by forming the first metal-containing layer 14 and the second metal-containing layer 15 on the reusable core 11 in this order from the inside out, it is possible to remanufacture the medium 10 having the desired configuration.

[0038] It is not necessary to peel off all of the metal-containing layers that make up the shell of media 10. If the constituent elements of first metal-containing layer 14 are selected to have high corrosion resistance and the thickness of first metal-containing layer 14 is made relatively thicker than the thickness when the first metal-containing layer is peeled off, first metal-containing layer 14 can be left attached to the core, and only second metal-containing layer 15 can be peeled off.

[0039] In this case, media 10 having a desired configuration can be re-manufactured simply by forming second metal-containing layer 15 on the surface of first metal-containing layer 14 attached to the core.

[0040] The above-mentioned peeling can be carried out by, for example, a reverse electrolysis method, a melting method, or a chemical polishing immersion method.

[0041] In the reverse electrolysis method, as shown in Fig. 9, the arrangement of the cathode electrode 4 and the anode electrode 5 shown in Fig. 1 is reversed, and a voltage is applied between the electrodes using a power source 7a to dissolve the metal plating layer 20 (see Fig. 5) formed on the surface of the medium 10 and at least one metal-containing layer constituting the medium 10 into the electrolytic solution 1a. After dissolution, the metal component is deposited on the cathode electrode 4 side. As the electrolytic solution 1a, for example, dilute nitric acid, dilute sulfuric acid, dilute alkali, or diluted plating solution can be used.

[0042] In this case, it is preferable that the core 11 has an insulating surface to avoid the possibility that not only the metal-containing layer constituting the shell of the medium 10 but also the components of the core 11 will be eluted, making it difficult to reuse the core 11. From the viewpoint of improving insulation, it is more preferable that the core 11 is insulating not only on its surface but also inside, and it is even more preferable that the entire core 11 is insulating. Here, "insulating" with respect to the core refers to a state in which current generated by voltage application does not flow or flows little through the core, thereby preventing elution of the components of the core 11 from the core surface into the electrolyte.

[0043] In the melting method, after plating is performed using the plating apparatus shown in Fig. 1, the object 6 to be plated with the plating layer and the media 10 with the plating layer 20 (see Fig. 5) are removed from the barrel 3. Then, the removed media 10 with the plating layer 20 is subjected to a heat treatment for melting at, for example, 1700°C in a melting furnace.

[0044] In this case, to avoid the possibility that not only the metal-containing layer constituting the shell of the media 10 but also the components of the core 11 melt, making it difficult to reuse the core 11, it is preferable that the melting point of the core 11 be higher than that of the metal-containing layer of the multi-layer body 13. The above-mentioned ceramics can be used for the core 11. Examples of ceramics that can be used include alumina, which has a melting point of 2070°C, and zirconia, which has a melting point of 2700°C.

[0045] In the chemical polishing immersion method, after plating is performed using the plating apparatus shown in FIG. 1, the workpiece 6 with the plating layer and the media 10 with the plating layer 20 (see FIG. 5) are removed from the barrel 3. The removed media 10 with the plating layer 20 is then immersed in a chemical polishing solution. Examples of chemical polishing solutions include nitric acid, hydrochloric acid, SPS (sodium persulfate), a sulfuric acid peraqueous solution, and a phosphoric acid peraqueous solution. The chemical polishing solution can also be called an etching solution. Alternatively, the layer can be removed by reverse electrolytic barrel treatment.

[0046] In this case, to avoid the possibility that not only the metal-containing layer constituting the shell of the media 10 but also the components of the core 11 are eluted, making it difficult to reuse the core 11, it is preferable that the core 11 have a chemical-resistant surface. From the viewpoint of improving chemical resistance, it is more preferable that the core 11 has chemical resistance not only on its surface but also inside, and it is even more preferable that the entire core 11 has chemical resistance. Here, "chemical resistance" with respect to the core refers, in a broad sense, to the durability of the core components against chemicals such as chemical polishing solutions. In a narrow sense, "chemical resistance" with respect to the core refers to a state in which the core components are not eluted or are difficult to elute in media with a plated layer when immersed in a chemical polishing solution.

[0047] The first metal-containing layer 14 may have a thickness of 0.01 μm or more and 1 μm or less. A thickness of 0.01 μm or more ensures a predetermined electrical conductivity and adhesion to the surface of the core 11. This prevents the second metal-containing layer 15 from peeling off along with the first metal-containing layer 14. As a result, the media 10 can perform its functions optimally, and a plating layer can be formed optimally on the plated object 6 within the barrel 3.

[0048] Furthermore, by having a thickness of 1 μm or less, it is possible to prevent the media 10 itself from becoming heavy and making it difficult to balance the object 6 to be plated and the media 10. This allows the object 6 to be plated and the media 10 to be mixed uniformly within the barrel 3, stabilizes the current flow, and makes it possible to make the thickness of the plating layer formed on the object 6 to be plated uniform.

[0049] The second metal-containing layer 15 may have a thickness of 0.1 μm or more and 10 μm or less. A thickness of 0.1 μm or more can ensure the desired electrical conductivity and other properties (such as oxidation resistance) and ensure adhesion to the surface of the first metal-containing layer 14. Furthermore, a thickness of 10 μm or less can prevent the media 10 itself from becoming heavy, making it difficult to balance the object 6 to be plated with the media 10. This allows the object 6 to be plated and the media 10 to be mixed uniformly within the barrel 3, stabilizes electrical conduction, and ensures a uniform thickness of the plating layer formed on the object 6 to be plated.

[0050] The media 10 may be spherical as shown in Figure 1, or may have the same shape as the object to be plated (such as an electronic component) (e.g., a rectangular parallelepiped). This allows the mixed state of the object to be plated 6 and the media 10 in the barrel 3 to be suitably changed, thereby improving the deposition rate of the plating layer on the object to be plated 6 and enabling the plating layer to be deposited uniformly.

[0051] It is preferable that granular insulators are further contained within the barrel 3. The presence of such insulators can prevent unnecessary bonding between the media 10 and the object 6 (electronic component, etc.), thereby improving the quality of the plating layer on the object 6.

[0052] In addition, in an electroless plating process, when the first metal-containing layer, which can serve as a base layer, and the second metal-containing layer 15, which is a separate layer, both contain Ni components, the state of each layer can be confirmed based on the amount of impurities and crystallinity in the first metal-containing layer.

[0053] The state of each layer can be confirmed by taking a cross section of each metal-containing layer and performing element mapping using EDX and WDX. In electroless plating, the first metal-containing layer serving as an underlayer may contain B (boron) and / or P (phosphorus), so it is possible to determine that the layer containing B and / or P is the underlayer.

[0054] Furthermore, when forming a metal-containing layer by a method other than plating, it is possible to use FIB-SIM to capture a cross section, check the crystallinity, and identify each layer based on the difference in orientation between the first metal-containing layer 14 and the second metal-containing layer 15.

[0055] Second Embodiment The second embodiment is described below. The second embodiment differs from the first embodiment in that the multi-layer structure 13 of the shell 12 has a third metal-containing layer 16 located outside the second metal-containing layer 15.

[0056] FIG. 3 is a cross-sectional view schematically showing a plating medium according to a second embodiment of the present invention.

[0057] The third metal-containing layer 16 may contain at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt, and Au. The third metal-containing layer 16 containing this metal element may be a dry-plated layer or a wet-plated layer. As with the second metal-containing layer 15, the dry-plated layer may be formed on the surface of the formed second metal-containing layer 15 using at least one method selected from the group consisting of CVD, sputtering, PVD, vacuum deposition, hot-dip plating, thermal spraying, and lightening (see FIG. 7 ). The third metal-containing layer 16 may also be formed using methods other than plating, such as painting, sol-gel deposition, electrolytic polymerization, and / or electroforming.

[0058] When third metal-containing layer 16 is a wet-plated layer, it can be formed by performing electroless plating or electrolytic plating on the surface of second metal-containing layer 15 (see FIG. 7 ). In the case of electroless plating, a catalyst may be applied to the surface of second metal-containing layer 15, and the catalyst may contain at least one catalyst selected from the group consisting of Pd, Ag, and Ni.

[0059] As described above, in this embodiment, compared to the first embodiment, the presence of a multilayer structure of three (i.e., two or more) metal-containing layers allows the three metal-containing layers to have the same or different properties, which makes it possible to provide even more suitable conductivity and / or properties other than conductivity compared to the first embodiment.

[0060] 3, for example, the first metal-containing layer 14, the second metal-containing layer 15, and the third metal-containing layer 16 can all have conductive properties, which allows for more efficient electrical continuity between the object to be plated 6 and the cathode electrode 4. Furthermore, the first metal-containing layer 14 and the second metal-containing layer 15 can be primarily conductive, and the third metal-containing layer 16, which is the outermost layer, can have other properties in addition to conductivity, such as oxidation resistance.

[0061] Furthermore, after the metal plating layer 20 is formed not only on the object to be plated 6 but also on the surface of the media 10A (see Figure 7), the metal plating layer 20 is peeled off and at least two metal-containing layers that make up the shell 12 of the media 10A are peeled off, making it possible to reuse the media 10A.

[0062] 7, the metal plating layer 20 may be peeled off, and the three metal-containing layers 14, 15, and 16 that make up the shell of the media 10A may be peeled off, thereby making it possible to reuse the core 11 (corresponding to the core material) of the media 10A after the peeling.

[0063] The third metal-containing layer 16 may also have a thickness of 0.1 μm or more and 10 μm or less. A thickness of 0.1 μm or more can ensure the desired electrical conductivity and other properties (such as oxidation resistance) and ensure adhesion to the surface of the second metal-containing layer 15. A thickness of 10 μm or less can prevent the media 10A itself from becoming heavy, making it difficult to balance the object 6 to be plated with the media 10A.

[0064] [Third Embodiment] The third embodiment will be described below. The third embodiment differs from the second embodiment in that the multi-layer structure 13 of the shell 12 has a fourth metal-containing layer 17 located outside the third metal-containing layer 16.

[0065] FIG. 4 is a cross-sectional view schematically showing a plating medium according to a third embodiment of the present invention.

[0066] The fourth metal-containing layer 17 may contain at least one element selected from the group consisting of Sn, Pd, Pt, and Au. The fourth metal-containing layer 17 containing this metal element may be a dry-plated layer or a wet-plated layer. As with the third metal-containing layer 16, the dry-plated layer may be formed on the surface of the formed third metal-containing layer 16 using at least one method selected from the group consisting of CVD, sputtering, PVD, vacuum deposition, hot-dip plating, thermal spraying, and lightening (see FIG. 8 ). The fourth metal-containing layer 17 may also be formed using methods other than plating, such as painting, sol-gel deposition, electrolytic polymerization, and / or electroforming.

[0067] When fourth metal-containing layer 17 is a wet-plated layer, it can be formed by performing electroless plating or electrolytic plating on the surface of third metal-containing layer 16 (see FIG. 8 ). In the case of electroless plating, a catalyst may be applied to the surface of third metal-containing layer 16, and the catalyst may contain at least one catalyst selected from the group consisting of Pd, Ag, and Ni.

[0068] As described above, in this embodiment, compared to the second embodiment, the presence of a multilayer structure of four (i.e., two or more) metal-containing layers allows the four metal-containing layers to have the same or different properties, which makes it possible to provide even more suitable conductivity and / or properties other than conductivity compared to the second embodiment.

[0069] 4, for example, the first metal-containing layer 14, the second metal-containing layer 15, the third metal-containing layer 16, and the fourth metal-containing layer 17 can all have conductive properties. This allows for even more favorable electrical continuity between the object to be plated 6 and the cathode electrode 4. Furthermore, the first metal-containing layer 14 to the third metal-containing layer 16 can be primarily conductive, and the fourth metal-containing layer 17, which is the outermost layer, can have other properties in addition to conductivity, such as oxidation resistance.

[0070] Furthermore, after the metal plating layer 20 is formed not only on the object to be plated 6 but also on the surface of the media 10B (see Figure 8), the metal plating layer 20 is peeled off and at least three metal-containing layers that make up the shell 12 of the media 10B are peeled off, thereby making it possible to reuse the media 10B.

[0071] 8, the metal plating layer 20 may be peeled off and the four metal-containing layers 14 to 17 that make up the shell of the medium 10B may be peeled off, thereby making it possible to reuse the core 11 (corresponding to the core material) of the medium 10B after the peeling.

[0072] The fourth metal-containing layer 17 may also have a thickness of 0.1 μm or more and 10 μm or less. A thickness of 0.1 μm or more can ensure the desired electrical conductivity and other properties (such as oxidation resistance) and ensure adhesion to the surface of the third metal-containing layer 16. Furthermore, a thickness of 10 μm or less can prevent the media 10B itself from becoming heavy, making it difficult to balance the object 6 to be plated and the media 10B.

[0073] It should be noted that each embodiment and modification are merely examples, and the present invention is not limited to each embodiment and modification. Furthermore, each drawing is an example of the components, and does not limit the shape. Furthermore, partial substitution or combination of the configurations shown in different embodiments and modifications is possible. For example, while the above description is based on plating media used in plating equipment, the present invention is not limited to this, and media having the above characteristics and contained in solder materials, etc., may also be included in the scope of the present invention.

[0074] The present invention may take the following forms. <1> A plating media comprising a core and a shell provided on the surface of the core, the shell constituting a multi-layer structure of two or more metal-containing layers. <2> The plating media according to <1>, wherein the core has a surface with relatively higher chemical resistance than the multi-layer structure. <3> The plating media according to <1> or <2>, wherein the core has at least an insulating surface. <4> The plating media according to any one of <1> to <3>, wherein the melting point of the core is higher than the melting point of the metal-containing layer of the multi-layer structure. <5> The plating media according to any one of <1> to <4>, wherein the core is at least one selected from the group consisting of ceramic, resin, and glass. <6> The plating media according to <5>, wherein the ceramic includes at least one selected from the group consisting of alumina, zirconia, sapphire, yttria, magnetite, cermet, silicon carbide, silicon nitride, aluminum nitride, steatite, cordierite, and quartz glass. <7> The plating media according to any one of <1> to <6>, wherein the multilayer body includes a first metal-containing layer in contact with the core, the first metal-containing layer containing, as a main component, at least one element selected from the group consisting of Ni, Cu, Pd, Sn, Ag, Zn, Co, Au, Pt, In, and Bi. <8> The plating media according to <7>, wherein the first metal-containing layer contains, as a catalyst, at least one catalyst selected from the group consisting of Pd, Ag, and Ni. <9> The plating media according to <7> or <8>, wherein the first metal-containing layer has a thickness of 0.01 μm or more and 1 μm or less. <10> The plating media according to any one of <7> to <9>, wherein the multilayer body includes a second metal-containing layer located outside the first metal-containing layer, the second metal-containing layer containing at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt, and Au. <11> The plating media according to <10>, wherein the second metal-containing layer has a thickness of 0.1 μm or more and 10 μm or less.<12> The plating media according to <10> or <11>, wherein the multilayer structure includes a third metal-containing layer located outside the second metal-containing layer, and the third metal-containing layer contains at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt, and Au. <13> The plating media according to <12>, wherein the third metal-containing layer has a thickness of 0.1 μm or more and 10 μm or less. <14> A method for producing plating media, comprising the steps of preparing a core and forming a shell having a multilayer structure of two or more metal-containing layers on a surface of the core. <15> A method for recycling plating media, comprising a core and a shell provided on the surface of the core, the shell constituting a multilayer structure of two or more metal-containing layers, comprising the steps of peeling off the plated object located on the surface of the media and at least one metal-containing layer of the media after plating. <16> The method for reusing plating media according to <15>, wherein the plating object and the metal-containing layer are stripped by at least one method selected from the group consisting of reverse electrolysis, melting, and chemical polishing immersion.

[0075] 50 Plating apparatus 17 Fourth metal-containing layer 16 Third metal-containing layer 15 Second metal-containing layer 14 First metal-containing layer 13 Multilayer body 12 Shell 11 Core (corresponding to core material) 10 Conductive plating media 7, 7a Power source 6 Object to be plated 5 Anode electrode 4 Cathode electrode 3 Barrel 2 Plating bath 1 Plating solution 1a Electrolyte

Claims

1. A plating medium comprising a core and a shell provided on the surface of the core, the shell constituting a multi-layer body of two or more metal-containing layers.

2. The plating media of claim 1, wherein said core has a surface that is relatively more chemically resistant than said laminate.

3. The plating media according to claim 1 or 2, wherein the core has at least an insulating surface.

4. The plating media according to any one of claims 1 to 3, wherein the melting point of the core is higher than the melting point of the metal-containing layer of the laminate.

5. The plating media according to any one of claims 1 to 4, wherein the core is at least one selected from the group consisting of ceramic, resin and glass.

6. The plating media of claim 5, wherein the ceramic comprises at least one selected from the group consisting of alumina, zirconia, sapphire, yttria, magnetite, cermet, silicon carbide, silicon nitride, aluminum nitride, steatite, cordierite, and quartz glass.

7. The plating media according to any one of claims 1 to 6, wherein the laminate includes a first metal-containing layer in contact with the core, the first metal-containing layer containing, as a main component, at least one element selected from the group consisting of Ni, Cu, Pd, Sn, Ag, Zn, Co, Au, Pt, In, and Bi.

8. The plating media of claim 7, wherein the first metal-containing layer contains at least one catalyst selected from the group consisting of Pd, Ag, and Ni as a catalyst.

9. The plating media according to claim 7 or 8, wherein the first metal-containing layer has a thickness of 0.01 μm or more and 1 μm or less.

10. The plating media according to any one of claims 7 to 9, wherein the laminate includes a second metal-containing layer located outside the first metal-containing layer, and the second metal-containing layer includes at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt and Au.

11. The plating media of claim 10, wherein the second metal-containing layer has a thickness of at least 0.1 μm and not more than 10 μm.

12. The plating media according to claim 10 or 11, wherein the laminate includes a third metal-containing layer located outside the second metal-containing layer, and the third metal-containing layer includes at least one element selected from the group consisting of Sn, Ni, Cu, Pd, Pt and Au.

13. The plating media of claim 12, wherein the third metal-containing layer has a thickness of 0.1 μm or more and 10 μm or less.

14. A method for preparing plating media, comprising the steps of providing a core and forming a shell having a multilayer structure of two or more metal-containing layers on the surface of the core.

15. A method for reusing plating media comprising a core and a shell provided on the surface of the core, the shell constituting a laminate of two or more metal-containing layers, comprising peeling off the plated object located on the surface of the media and at least one metal-containing layer of the media after plating.

16. The method for recycling plating media according to claim 15, wherein stripping of the plated article and the metal-containing layer is performed by at least one method selected from the group consisting of reverse electrolysis, melting, and chemical abrasive immersion.

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