JP2010216003A - Copper material for plating, method for manufacturing copper material for plating, and method for manufacturing copper-plated material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a copper material for plating, which has a large ratio S/V of a surface area S to a volume V, can effectively supply copper ions into a plating solution formed of a sulfuric acid solution or the like, and can efficiently form a plated film while suppressing a production of a copper powder; a method for manufacturing the copper material for plating; and a method for manufacturing a copper-plated material using the copper material for plating. <P>SOLUTION: The copper material 10 for plating is used for supplying the copper ions into the plating solution, and is made of a copper wire which is spirally wound to form a coil body. Here, it is preferable that the outside diameter of the copper wire is controlled to 1.5-5 mm, and the tensile strength of the copper wire is controlled to 350 MPa or higher. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a copper material for plating used as a copper ion supply source in electrolytic plating of copper, a method for producing a copper material for plating, and a method for producing a copper plating material using the copper material for plating.

Conventionally, as a method of copper plating on a printed wiring board such as a mobile phone or a computer, while immersing copper as a soluble anode in a plating tank in which a plating solution such as a dilute sulfuric acid solution containing copper ions is stored, Electroplating in which a printed wiring board is immersed as a cathode and the anode and the cathode are energized is widely used. Thus, in the electroplating using the soluble anode, the copper used as the anode is dissolved in the dilute sulfuric acid solution to become copper ions, and copper is electrodeposited on the surface of the printed wiring board used as the cathode. Become. That is, the plating copper material is dissolved by electrolysis.
Moreover, instead of the soluble anode, electrolytic plating in which an insoluble anode such as iridium oxide is immersed in a plating tank is also widely used. In this case, it is necessary to supply copper ions to the plating solution in the plating tank by dissolving copper in a sulfuric acid solution or the like. Here, when copper is dissolved in a sulfuric acid solution or the like, a method utilizing electrolysis or a method utilizing a chemical reaction may be mentioned.

As a copper ion supply source for performing such electrolytic plating, for example, as disclosed in Patent Documents 1 and 2, a copper material (copper ball for plating) formed in a ball shape or a circle obtained by cutting a copper wire Columnar copper is widely used.
For example, when this plating copper ball is used as a soluble anode, a basket made of a corrosion-resistant material such as Ti is placed in the plating tank, and the plating copper ball is inserted into the basket. It is said that. The copper balls for plating are gradually consumed as they dissolve in the plating solution. However, by continuously rolling the copper balls for plating into the Ti basket according to the amount consumed, electrolytic plating can be performed continuously. Is something that can be done.
On the other hand, when an insoluble anode is used, the copper balls for plating are dissolved in a sulfuric acid solution or the like outside the plating tank and are sequentially supplied into the plating tank.

  The above-mentioned copper balls for plating are made of low oxygen copper, oxygen-free copper, phosphorus deoxidized copper or the like having an oxygen content of 20 ppm or less, and have a diameter of about 10 mm to 60 mm. For example, as shown in Patent Documents 3 and 4, such a copper ball for plating is obtained by cutting a long copper rod material to obtain a substantially cylindrical copper rod material, and rolling the copper rod material or It is formed by forging.

By the way, when the copper material for plating is dissolved by the electrolytic method, a black film mainly composed of copper oxide is formed on the surface of the copper material for plating. It is known that a black film formed uniformly and thinly has the effect of suppressing the following disproportionation reaction, preventing passivation and assisting good dissolution.
2Cu ⁺ → Cu ²⁺ + Cu (fine powder)
However, the flow of the plating solution is weak, and when the divalent copper ions generated by electrolysis stay near the surface of the plating copper material and the concentration of the divalent copper ions near the surface increases, monovalent copper ions are likely to be generated. Thus, the disproportionation reaction proceeds and a large amount of fine copper powder is generated. A large amount of fine copper powder is taken into the black film, and the black film grows thick and falls off the surface of the copper material for plating, generating black sludge-like anode slime. Such a thickly grown black film or anode slime inhibits the dissolution of the plating copper material and adversely affects the plating quality. Therefore, in Patent Document 5, the plating copper material is vibrated, the plating solution is sprayed, or ultrasonic waves are applied to remove the black film and anode slime generated on the surface of the plating copper material. It has been proposed. Patent Document 6 proposes removing black film and anode slime generated on the surface of the copper material for plating by bubbling.

JP 2000-054199 A JP 2003-328198 A JP 2006-297479 A JP 2006-225746 A JP 2008-081777 A JP 09-241894 A

By the way, when the copper balls for plating described in Patent Documents 1-4 are dissolved with a sulfuric acid solution or the like, the one having a larger area in contact with the sulfuric acid solution or the like is efficiently dissolved. That is, as the ratio S / V between the surface area S and the volume V increases, it becomes possible to efficiently supply copper ions into the plating solution.
However, the above-described copper balls for plating have a problem that the ratio S / V between the surface area S and the volume V becomes relatively small and copper ions cannot be supplied efficiently. In addition, when using a cylindrical copper material, etc., if a plurality of plating copper materials are inserted into a Ti basket, etc., the copper ions for plating do not come into contact with the sulfuric acid solution, etc. The supply efficiency will be reduced.

  Here, when the copper material for plating is dissolved by the electrolytic method, as described above, a large amount of copper powder is generated, and the black film grows thick and anode slime is generated. It is necessary to provide a mechanism for removing the black film and anode slime as shown in FIG. For this reason, there existed a problem that plating operation became complicated and plating could not be performed efficiently.

  The present invention has been made in view of the above-described circumstances, and the ratio S / V between the surface area S and the volume V is large, and copper ions can be efficiently supplied into a plating solution made of a sulfuric acid solution or the like. Copper plating material capable of being efficiently plated while suppressing generation of copper powder, a method for producing the copper material for plating, and production of a copper plating material using the copper material for plating It aims to provide a method.

In order to solve the above-described problems, a copper material for plating according to the present invention is a copper material for plating used when supplying copper ions into a plating solution, and is a coil in which a copper wire is wound spirally. It is characterized by being a body.
In the plating copper material of this configuration, since the copper wire is a coil body wound spirally, the outer peripheral surface of the copper wire is exposed to the outer peripheral side and the inner peripheral side of the coil body, The ratio S / V between the surface area S and the volume V increases. Therefore, copper is easily dissolved in a plating solution such as a sulfuric acid solution, and copper ions can be efficiently supplied into the plating solution. Moreover, since it contacts with the plating solution on the inner peripheral surface of the coil body, even if a plurality of copper materials for plating overlap, copper is dissolved from the inner peripheral surface of the coil body, Copper ions can be supplied more efficiently.

Here, it is preferable that the outer diameter of the copper wire constituting the coil body is 1.5 mm or more and 5 mm or less.
In the copper material for plating of this configuration, since the outer diameter of the copper wire is 1.5 mm or more, the rigidity of the copper wire is ensured, and even when a plurality of copper materials for plating are overlapped, plating is performed. The copper material is not deformed so as to be crushed, and can be dissolved by contacting with a plating solution such as a sulfuric acid solution on the inner peripheral side of the plating copper material. Moreover, since the outer diameter of the copper wire is 5 mm or less, the ratio S / V between the surface area S and the volume V can be increased, and the plating copper material can be efficiently dissolved.

Furthermore, it is preferable that the tensile strength of the copper wire is 350 MPa or more.
In the copper material for plating of this configuration, since the tensile strength of the copper wire is 350 MPa or more, the rigidity of the copper wire is ensured, and even if a plurality of copper materials for plating overlap, The material is not deformed so as to be crushed, and can be dissolved by being brought into contact with a plating solution such as a sulfuric acid solution on the inner peripheral side of the plating copper material. In addition, in order to ensure that this effect is achieved, it is more preferable that the tensile strength of the copper wire is 400 MPa or more.

The method for producing a copper material for plating according to the present invention is a method for producing a copper material for plating, which produces the above-described copper material for plating, and a copper wire supplying step for supplying a copper wire, and the supplied copper wire And a cutting step of cutting the copper wire after forming a coil body having a predetermined length.
According to the method for producing a copper material for plating of this configuration, it is possible to continuously produce a copper material for plating which is a coil body in which a copper wire is spirally wound.

The method for producing a copper plating material according to the present invention includes immersing a material to be plated as a cathode in a plating tank in which a plating solution is stored, immersing a soluble anode in the plating tank, and energizing the anode and the cathode. A method for producing a copper plating material in which copper is electrodeposited on the surface of the material to be plated, wherein the above-described copper material for plating is immersed in the plating tank as the soluble anode.
According to the method for producing a copper plating material having this configuration, by using the above-described copper material for plating as a soluble anode, it becomes possible to efficiently supply copper ions into the plating solution, thereby efficiently performing the copper plating. Can be performed.

  Also, since the plating copper material described above is used as a soluble anode and the plating copper material is dissolved by an electrolytic method, a black film grows thick on the surface of the plating copper material, and anode slime is generated. It becomes easy. Here, in the present invention, since the copper material for plating is a coil body in which a copper wire is spirally wound, the plating solution passes through the inner peripheral side of the coil body, thereby ensuring the flow rate of the plating solution. Then, the concentration of divalent copper ions does not become higher than necessary around the copper material for plating, the generation of copper powder is suppressed, and the growth of black film and the formation of anode slime are suppressed. Therefore, it is not necessary to provide a mechanism for removing the black film or the like, and the plating operation can be performed efficiently.

The method for producing a copper plating material according to the present invention includes immersing a material to be plated as a cathode in a plating tank in which a plating solution is stored, immersing an insoluble anode in the plating tank, and energizing the anode and the cathode. A method for producing a copper plating material in which copper is electrodeposited on the surface of the material to be plated, wherein a plating solution supplied with copper ions is produced by dissolving the copper material for plating described above. It is characterized by being supplied to a plating tank.
According to the method for producing a copper plating material of this configuration, the above-described plating copper material is dissolved to produce a plating solution supplied with copper ions, and this plating solution is supplied to the plating tank. Even if it is a case where it uses, it becomes possible to perform copper plating efficiently.

The method for producing a copper plating material according to the present invention includes immersing a material to be plated as a cathode in a plating tank in which a plating solution is stored, immersing an insoluble anode in the plating tank, and energizing the anode and the cathode. A method for producing a copper plating material in which copper is electrodeposited on the surface of the material to be plated, wherein the copper material for plating according to any one of claims 1 to 3 is dissolved by a chemical reaction, A plating solution supplied with copper ions is generated, and this plating solution is supplied to the plating tank.
According to the method for producing a copper plating material of this configuration, since the plating copper material is dissolved using a chemical reaction, the black film and the anode slime are not generated, and the plating copper material is dissolved well. It becomes possible. Further, as described above, since the ratio S / V of the surface area S to the volume V of the plating copper material is larger than that of the conventional plating copper ball, the reaction area is ensured and the dissolution rate can be improved. .

  According to the present invention, the ratio S / V between the surface area S and the volume V is large, copper ions can be efficiently supplied into the plating solution made of a sulfuric acid solution, and the generation of copper powder is suppressed. It is possible to provide a plating copper material that can be efficiently plated, a method for producing the copper material for plating, and a method for producing a copper plating material using the copper material for plating.

It is a side view of the copper material for plating which is embodiment of this invention. It is a front view of the copper material for plating which is an embodiment of the present invention. It is a flowchart of the manufacturing method of the copper material for plating which is embodiment of this invention. It is explanatory drawing which shows the manufacturing method of the copper plating material using the copper material for plating which is embodiment of this invention. It is explanatory drawing which shows the manufacturing method of the other copper plating material using the copper material for plating which is embodiment of this invention. It is explanatory drawing which shows the manufacturing method of the other copper plating material using the copper material for plating which is embodiment of this invention. It is a side view of the copper material for plating which is other embodiment of this invention. It is a side view of the copper material for plating which is other embodiment of this invention. It is a side view of the copper material for plating which is other embodiment of this invention. It is a side view of the copper material for plating which is other embodiment of this invention. It is explanatory drawing of the test apparatus of Example 2. FIG. It is explanatory drawing of the test apparatus of Example 3. FIG.

  Hereinafter, a plating copper material and a plating copper material manufacturing method according to an embodiment of the present invention, and a copper plating material manufacturing method using the plating copper material of the present invention will be described with reference to the accompanying drawings. This will be described in detail.

  The outline of the copper material 10 for plating which is this embodiment is shown in FIG.1 and FIG.2. The copper material 10 for plating which is this embodiment is made into the coil body by which the copper wire was helically wound as shown in FIG.1 and FIG.2, and the external shape has comprised the cylindrical shape in this embodiment. .

Here, the diameter r of the copper wire forming the plating copper material 10 is set in a range of 1.5 mm ≦ r ≦ 5 mm, and in this embodiment, 2.6 mm ≦ r ≦ 3.2 mm. Yes.
The copper wire is made of low-oxygen copper or oxygen-free copper having a copper purity of 99.96% or more and an oxygen content of 20 ppm or less, and the tensile strength TS of the copper wire is TS ≧ 350 MPa.

Further, the outer diameter Ro of the cylinder formed by the copper material 10 (coil body) for plating is set within the range of 4.5 mm ≦ Ro ≦ 20 mm, and the inner diameter Ri is set within the range of 1.5 mm ≦ Ri ≦ 16 mm. Has been.
Furthermore, the length L of the plating copper material 10 (coil body) is set within a range of 5 mm ≦ L ≦ 50 mm. The pitch P of the wound copper wire is set within the range of r + 0.1 mm ≦ P ≦ 3 × rmm with respect to the diameter r of the copper wire, specifically 1.6 mm ≦ P ≦ 15 mm. It is set within the range.

Below, the manufacturing method of the copper material for plating which is this embodiment is demonstrated using the flowchart of FIG.
First, a copper wire made of low-oxygen copper or oxygen-free copper having a copper purity of 99.96% or more and an oxygen content of 20 ppm or less and having a diameter r in a range of 1.5 mm ≦ r ≦ 5 mm is produced. (Copper wire production process S1). In order to efficiently produce such a copper wire, for example, a belt-type continuous casting machine is used to continuously produce a long bar-shaped ingot, and the rod-shaped ingot is continuously rolled to produce a copper wire. Produces rough wire. Further, it is processed into a hard copper wire by a cold drawing process. At this time, rolling conditions, heat treatment conditions, cold wire drawing process conditions, and the like are set so that the tensile strength TS of the copper wire satisfies TS ≧ 350 MPa, and more preferably TS ≧ 400 MPa.

Next, the hard copper wire whose diameter r is in the range of 1.5 mm ≦ r ≦ 5 mm is supplied to the coil forming machine (copper wire supplying step S2).
In the coil forming machine, the coil body is formed by sequentially bending the copper wire while feeding the copper wire (coil forming step S3).
And a copper wire is cut | disconnected at the time of processing the copper wire of predetermined length (cutting process S4).
Thus, the copper material 10 for plating which is this embodiment is produced.

Below, the manufacturing method of the copper plating material using the copper material 10 for plating which is this embodiment is demonstrated.
In FIG. 4, the example which used the copper material 10 for plating which is this embodiment as a soluble anode is shown.
This plating apparatus 20 accommodates a plating tank 21 in which a plating solution 2 made of a sulfuric acid solution or the like is stored, a material 6 to be plated on which a copper plating film 7 is formed, and a copper material 10 for plating according to this embodiment. And a basket 23. The basket 23 is made of a corrosion resistant material such as Ti.

Here, the material 6 to be plated is a cathode, and the copper material 10 for plating accommodated in the basket 23 is a soluble anode, and the cathode and the anode are energized.
Then, the copper material 10 for plating accommodated in the basket 23 is dissolved in the plating solution 2, so that copper ions are supplied into the plating solution 2, and this copper ion is applied to the surface of the cathode (material to be plated 6). Electrodeposition is performed, and a copper plating film 7 is formed on the surface of the material 6 to be plated.
In this case, as the formation of the copper plating film 7 proceeds, the plating copper material 10 gradually dissolves and decreases. Therefore, it is preferable to provide a means for supplying the plating copper material 10 into the basket 23 as appropriate. .

Next, FIG. 5 shows an example in which copper ions are supplied using the plating copper material 10 according to the present embodiment and copper plating is performed using an insoluble anode.
The plating apparatus 30 includes a plating tank 31 in which a plating solution 2 made of a sulfuric acid solution or the like is stored, a material to be plated 6 on which a copper plating film 7 is formed, an insoluble anode 33 made of iridium oxide, and the like. A copper ion supply device 40 that supplies copper ions therein and a communication path 37 that connects the copper ion supply device 40 and the plating tank 31 are provided.

The copper ion supply device 40 is provided in an ion generation tank 41 in which the plating solution 2 is stored, a hydrogen ion exchange membrane 45 that partitions the ion generation tank 41 into a cathode chamber 41A and an anode chamber 41B, and the cathode chamber 41A. And a basket 43 that is disposed in the anode chamber 41B and accommodates the copper material for plating 10 according to the present embodiment.
Here, the communication path 37 that connects the copper ion supply device 40 and the plating tank 31 is connected to the anode chamber 41 </ b> B of the ion generation tank 41.

  In the copper ion supply device 40, electricity is supplied between the basket 43 and the plating copper material 10 accommodated in the basket 43 as the anode and the cathode portion 44 of the cathode chamber 41 </ b> A. Then, the copper material 10 for plating dissolves in the plating solution 2 and copper ions are supplied into the plating solution 2. Here, the hydrogen ions existing in the anode chamber 41B pass through the hydrogen ion exchange membrane 45 and enter the cathode chamber 41A, and are released to the outside as hydrogen gas from the surface of the cathode portion 44.

  The plating solution 2 supplied with copper ions in the anode chamber 41 </ b> B is supplied into the plating tank 31 through the communication path 37. In this plating tank 31, by applying current to the insoluble anode 33 and the material to be plated 6 that is the cathode, copper ions in the plating solution 2 are electrodeposited on the surface of the cathode (material to be plated 6). A copper plating film 7 is formed on the surface of the material 6.

  According to the plating copper material 10 of this embodiment having such a configuration, since the copper wire is a coil body wound spirally, the outer peripheral surface of the copper wire is the outer peripheral side of the coil body and As a result, the ratio S / V between the surface area S and the volume V increases. Therefore, copper is easily dissolved in the plating solution 2 such as a sulfuric acid solution, and copper ions can be efficiently supplied into the plating solution 2. Moreover, since it contacts with the plating solution 2 in the inner peripheral surface of the copper material 10 for plating, even if it inserts the several copper material 10 for plating in the baskets 23 and 43, the copper material 10 for plating which makes a cylindrical shape Since copper is dissolved from the inner peripheral surface, the supply of copper ions into the plating solution 2 can be performed more efficiently.

In the present embodiment, the outer diameter r of the copper wire is set within a range of 1.5 mm ≦ r ≦ 5 mm, and more specifically within a range of 2.6 mm ≦ r ≦ 3.2 mm. Since it is set, the rigidity of the copper wire is ensured, and even if a plurality of plating copper materials 10 are overlapped, the plating copper material 10 is not deformed so as to be crushed. It can be dissolved by contacting with the plating solution 2 on the peripheral side. Further, the ratio S / V between the surface area S and the volume V can be increased, and the plating copper material 10 can be efficiently dissolved.
Further, the copper wire whose outer diameter r is set within the range of 2.6 mm ≦ r ≦ 3.2 mm is obtained by the continuous casting rolling means using the belt wheel type continuous casting machine and the cold wire drawing process as described above. Since it can produce well, the copper material 10 for plating which is this embodiment can be produced efficiently.

  Moreover, since the tensile strength TS of the copper wire is TS ≧ 350 MPa, more preferably TS ≧ 400 MPa, the rigidity of the copper wire is ensured, and even when a plurality of plating copper materials 10 overlap, The plating copper material 10 is not deformed so as to be crushed, and can be dissolved by being brought into contact with the plating solution 2 on the inner peripheral side of the plating copper material 10. Moreover, a copper wire can be wound helically and formed into a coil body relatively easily.

  Furthermore, in this embodiment, the pitch P of the wound copper wire is set within the range of r + 0.1 mm ≦ P ≦ 3 × rmm with respect to the diameter r of the copper wire. Since it is set within the range of 6 mm ≦ P ≦ 15 mm, the plating solution 2 such as sulfuric acid solution is introduced into the inner peripheral side of the plating copper material 10 from the gap between adjacent copper wires, and the plating copper material 10 Dissolution is promoted. Moreover, the copper wire of the other copper material 10 for plating is not pinched | interposed into the said clearance gap, the copper materials 10 for metal plating do not intertwine, and can melt | dissolve the copper material 10 for plating.

  Moreover, according to the manufacturing method of the copper material 10 for plating which is this embodiment, since a copper wire is continuously introduce | transduced into a coil molding machine and the copper material 10 for plating which consists of a coil body is shape | molded, this embodiment It is possible to efficiently produce the copper material 10 for plating. Furthermore, in the present embodiment, since a long bar-shaped ingot is continuously produced using a belt wheel type continuous casting machine and a continuous casting rolling means for continuously rolling the bar-shaped ingot is used, A high-quality copper wire can be produced efficiently at low cost, and the copper material for plating 10 according to the present embodiment can be produced more efficiently.

Furthermore, in the manufacturing method of the copper plating material using the copper material 10 for plating which is this embodiment, the copper material 10 for plating melt | dissolves efficiently in the plating solution 2, and copper ion is supplied in the plating solution 2. Therefore, copper plating can be performed efficiently.
Moreover, as shown in FIG. 5, when the copper ion supply apparatus 40 is used, also in the manufacturing method of the copper plating material using the insoluble anode 33, the copper material 10 for plating which is this embodiment is used. can do.

  Moreover, in the manufacturing method of the copper plating material using the copper material 10 for plating which is this embodiment, since the copper material 10 for plating is melt | dissolved by the electrolytic method, a black film is on the surface of the copper material 10 for plating. It grows thick and tends to generate anode slime. Here, in this embodiment, since the plating copper material 10 is a coil body in which a copper wire is spirally wound, the plating solution 2 may pass through the inner peripheral side of the plating copper material 10. And the flow rate of the plating solution 2 is ensured. Thereby, the density | concentration of a bivalent copper ion does not become higher than necessary around the copper material 10 for plating, generation | occurrence | production of copper powder is suppressed, and the growth of a black film and the production | generation of anode slime are suppressed.

Next, FIG. 6 shows an example in which the plating copper material 10 according to the present embodiment is dissolved by a chemical reaction to supply copper ions and copper plating is performed using an insoluble anode.
The plating apparatus 90 includes a plating tank 91 in which a plating solution 2 made of a sulfuric acid solution or the like is stored, a material to be plated 6 on which a copper plating film 7 is formed, an insoluble anode 93 made of iridium oxide, and the like. A copper ion supply device 96 that supplies copper ions to the metal, a communication path 94 that connects the copper ion supply device 96 and the plating tank 91, and a pump 95 that circulates the plating solution 2 are provided.
The copper ion supply device 96 includes an ion generation tank 97 in which the plating solution 2 is stored, and a basket 98 that is immersed in the plating solution 2 in the ion generation tank 97.

In the copper ion supply device 96, the copper material for plating 10 according to the present embodiment is accommodated in the basket 98 and immersed in the plating solution 2. Then, the copper material for plating 10 is dissolved in the plating solution 2 by the following chemical reaction, and copper ions are supplied into the plating solution 2.
Cu + 2Fe ³⁺ → Cu ²⁺ + 2Fe ²⁺
The plating solution 2 supplied with copper ions in the ion supply tank 97 is supplied to the plating tank 91 through the communication path 94. In this plating tank 91, by energizing the insoluble anode 93 and the material to be plated 6 that is the cathode, copper ions in the plating solution 2 are electrodeposited on the surface of the material to be plated 6, and A copper plating film is formed on the surface.

  According to the copper plating material manufacturing method using the plating copper material 10 according to the present embodiment having such a configuration, the plating copper material 10 is a coil body in which a copper wire is spirally wound. Therefore, the outer peripheral surface of the copper wire is exposed on the outer peripheral side and the inner peripheral side of the coil body, and the ratio S / V between the surface area S and the volume V increases. Here, in this embodiment, since the copper material 10 for plating is dissolved using the oxidation-reduction reaction of iron ions, the dissolution rate greatly depends on the area where the chemical reaction occurs. Therefore, when the ratio S / V between the surface area S and the volume V is increased, the dissolution rate can be significantly improved. Furthermore, since the copper material 10 for plating is a coil body in which a copper wire is spirally wound, the flow of the plating solution 2 on the surface of the copper material 10 for plating becomes smooth, and the supply of copper and iron ions is possible. This is done quickly and the dissolution rate of copper is further improved. This is because the copper dissolution reaction is a diffusion-controlled reaction governed by the supply rate of copper and iron ions.

As mentioned above, although the manufacturing method of the copper material for plating which is embodiment of this invention, the copper material for plating, and the copper plating material using the copper material for plating of this invention were demonstrated, this invention is this It is not limited and can be changed as appropriate without departing from the technical idea of the invention.
For example, the copper material for plating has been described as being produced by coil-forming a copper wire made of low-oxygen copper or oxygen-free copper. However, the present invention is not limited to this, and phosphorus is 0.03% by mass. You may coil-form the copper wire which consists of a phosphorus containing copper alloy containing 0.08 mass% or less above. Furthermore, the copper material for plating may be made of tough pitch copper (TPC) or high-purity copper (5N copper, 6N copper, etc.) having a purity of 99.999% or more excluding gas components.

In particular, when the plating copper material is dissolved by electrolysis, it is preferable to use a plating copper material made of a phosphorus-containing copper alloy containing phosphorus as described above. In this case, a black film is formed uniformly and thinly on the surface of the copper material for plating, and the disproportionation reaction is suppressed by this black film, thereby preventing passivation and improving the copper material for plating. It can be dissolved.
On the other hand, when the plating copper material is dissolved by a chemical reaction, it is not necessary to use a black film. Therefore, it is preferable to use a plating copper material made of oxygen-free copper or the like.

  Moreover, about the to-be-plated material 6, it does not specifically limit, In the copper plating with respect to various to-be-plated materials, the copper material for plating of this invention can be used. For example, it can be used for copper plating on printed wiring boards, copper plating for semiconductors, copper plating on plastic materials, copper plating on steel plates, and the like.

  Further, although the outer shape has been described as a cylindrical shape, the present invention is not limited to this. For example, the outer shape may be a conical shape as shown in FIG. 7 or a central diameter as shown in FIG. May be reduced, or the center diameter may be increased as shown in FIG. Further, as shown in FIG. 10, the winding pitch P may be changed.

Furthermore, the configuration of the plating apparatus that performs copper plating is not limited to that described in FIGS. 4 and 5, and can be appropriately changed in design.
Moreover, although demonstrated as what produces copper wire by the continuous casting rolling means using a belt wheel type continuous casting machine, it is not limited to this, Copper wire is produced by other means, such as extrusion molding. May be.
Furthermore, in the copper ion supply apparatus 40 shown in FIG. 5, although copper ion was produced | generated by the electrolysis method, it is not limited to this, A copper material is hot concentrated sulfuric acid (for example, temperature 70 degreeC, density | concentration 98%). It is good also as a structure which produces | generates a copper ion using the method of making it soak and dissolve.

Further, in the copper ion supply device 96 shown in FIG. 6, it has been described that the plating copper material 10 is dissolved using the oxidation-reduction reaction of iron ions, but the present invention is not limited to this, and air or oxygen gas Copper ions may be generated by a method of supplying copper into the plating solution and oxidizing and dissolving copper with oxygen.
Furthermore, although it demonstrated as a structure which accommodates the copper material 10 for plating in the basket 98, and is immersed in the plating solution 2 in the ion generation tank 97, it is not limited to this, The copper material 10 for plating is directly attached. It may be immersed in the plating solution 2 in the ion generation tank 97.

Example 1
Table 1 shows the results of calculating the ratio S / V of the surface area S to the volume V for the plating copper material of the present invention and the conventionally used plating copper balls.
The conventional example was a copper ball for plating having a diameter of 11 mm, which is generally used widely.
As an example of the present invention, a copper wire having a diameter of 2.6 mm was made to have the same volume as the copper ball for plating described above and wound in a coil shape.

  In the present invention example, the ratio S / V of the surface area S to the volume V is about 2.85 times compared to the conventional example, the contact area with the plating solution is increased, and dissolution into the plating solution is achieved. Was confirmed to be promoted.

(Example 2)
Next, the copper material for plating of the present invention and the conventionally used copper ball for plating were compared and evaluated for dissolution rates when they were dissolved by a chemical reaction.
As shown in FIG. 11, a Ti basket 198 is immersed in the ion generation tank 197, and the plating copper material of the present invention and a conventionally used plating copper ball are accommodated in the Ti basket 198. The configuration. A cathode plate 106 and an insoluble anode 193 made of iridium oxide or the like were immersed in a plating tank 191 connected to the ion generation tank 197 by a communication path 194.

  Here, the conventional example is a copper ball for plating having a diameter of 11 mm, which is generally widely used. In addition, as an example of the present invention, a copper wire having a diameter of 2.6 mm was made to have the same volume as that of the above-described copper ball for plating and wound in a coil shape. 30 pieces of each of these copper materials for plating were accommodated in a Ti basket 198.

Moreover, the thing of the following compositions was used for the plating solution 102, the amount of the plating solution was 30 L, and the plating solution temperature was 21-25 degreeC.
_{CuSO 4 · 5H 2 O: 140} g / L
_{FeSO 4 · 7H 2 O: 20} g / L
H ₂ SO ₄ : 100 g / L
Cl ⁻ : 50 ppm

After adjusting the Fe ³⁺ initial concentration in the plating solution before the start of the test to 0.003 mol / L (calculated from the oxidation-reduction potential measured by the ORP meter 199), electrolysis was performed for 10A × 17 hours, and copper for plating before and after electrolysis The change in weight of the material was measured.
As a result, in the conventional example, the weight reduction amount was 10.7 g, whereas in the present invention example, the weight reduction amount was 35.7 g. As described above, it was confirmed that the example of the present invention was dissolved 3.34 times as compared with the conventional example.

Here, as described in Example 1, in the example of the present invention, the ratio S / V of the surface area S to the volume V is about 2.85 times that of the conventional example, but the dissolution amount is 3 .34 times. This is presumed to be because the supply of copper and iron ions was carried out smoothly by promoting the flow of the plating solution in addition to the effect of increasing the surface area.
Thus, the copper material for plating of the present invention is particularly effective when the copper material for plating is dissolved using a chemical reaction.

Example 3
Next, the amount of anode slime generated when the copper material for plating of the present invention and the conventionally used copper ball for plating were dissolved by electrolysis was compared and evaluated.
As shown in FIG. 12, the Ti basket 123 containing the plating copper material and the cathode plate 106 were immersed in the plating solution 102 and energized to dissolve the plating copper material 123. Then, the amount of slime after electrolysis for 1 week with current of 2.5 A was measured.
Here, the conventional example is a copper ball for plating having a diameter of 11 mm, which is generally widely used. In addition, as an example of the present invention, a copper wire having a diameter of 2.6 mm was made to have the same volume as that of the above-described copper ball for plating and wound in a coil shape. 30 pieces of each of these copper materials for plating were accommodated in the Ti basket 123.

Moreover, the thing of the following compositions was used for the plating solution, the plating solution quantity was 5 L, and the plating solution temperature was 21-25 degreeC.
_{CuSO 4 · 5H 2 O: 75} g / L
H ₂ SO ₄ : 180 g / L
Cl ⁻ : 50 ppm
Additive containing disulfide compound: 1.5 mL / L
Additives containing polyethylene glycol: 15 mL / L

  The amount of anode slime after electrolysis for one week was 2.53 g in the conventional example, and 1.08 g in the present invention example. Thus, even when the plating copper material is melted by an electrolytic method, the amount of anode slime generated can be suppressed by using the coiled copper plating material of the present invention. confirmed.

2 Plating solution 6 Material to be plated 10, 50, 60, 70, 80 Copper material for plating 20, 30, 90 Plating apparatus 21, 31, 91 Plating tank 23, 43 Basket 33 Insoluble anode 40, 90 Copper ion supply apparatus

Claims (7)

It is a copper material for plating used when supplying copper ions into the plating solution,
A copper material for plating, which is a coil body in which a copper wire is spirally wound.   The copper material for plating according to claim 1, wherein an outer diameter of the copper wire is 1.5 mm or more and 5 mm or less.   The copper material for plating according to claim 1 or 2, wherein the copper wire has a tensile strength of 350 MPa or more. It is a manufacturing method of the copper material for plating which manufactures the copper material for plating as described in any one of Claims 1-3,
A copper wire supplying step for supplying a copper wire; a coil forming step for winding the supplied copper wire into a coil; and a cutting step for cutting the copper wire after forming a coil body of a predetermined length. A method for producing a copper material for plating, comprising: In the plating tank in which the plating solution is stored, the material to be plated is immersed as a cathode, a soluble anode is immersed in the plating tank, and the anode and the cathode are energized to deposit copper on the surface of the material to be plated. A method for producing a copper plating material,
The copper material for plating as described in any one of Claims 1-3 as the said soluble anode is immersed in the said plating tank, The manufacturing method of the copper plating material characterized by the above-mentioned. In the plating tank in which the plating solution is stored, the material to be plated is immersed as a cathode, the insoluble anode is immersed in the plating tank, and the anode and the cathode are energized to deposit copper on the surface of the material to be plated. A method for producing a copper plating material,
A plating solution supplied with copper ions is generated by dissolving the copper material for plating according to any one of claims 1 to 3, and the plating solution is supplied to the plating tank. A method for producing a copper plating material. In the plating tank in which the plating solution is stored, the material to be plated is immersed as a cathode, the insoluble anode is immersed in the plating tank, and the anode and the cathode are energized to deposit copper on the surface of the material to be plated. A method for producing a copper plating material,
The plating copper material according to any one of claims 1 to 3 is dissolved by a chemical reaction to generate a plating solution to which copper ions are supplied, and the plating solution is supplied to the plating tank. The manufacturing method of the copper plating material characterized by the above-mentioned.

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