JPH01298195A - Method for plating wire or bar with copper - Google Patents

Abstract

PURPOSE:To stably and efficiently form copper plating having, satisfactory adhesion by spraying a plating soln. contg. CuSO4.5H2O, H2SO4 and FeSO4.7H2O each at a specified concn. on a travelling wire or bar to carry out preplating before electroplating with a copper sulfate plating soln. CONSTITUTION:A copper sulfate plating soln. 6 for preplating contg. >=0.5g/l CuSO4.5H2O, 0.1-400g/l H2SO4 and <=400g/l FeSO4.7H2O or further contg. 0.01-100g/l Cl<-> is prepd. The plating soln. 6 is poured into a treatment vessel 5, pumped up 3 and sprayed on a travelling wire 1 from nozzles 2 through a pipe 4 to preplate the wire 1. After washing with water from nozzles 7, prescribed electroplating is carried out with a copper sulfate plating soln. Waste water is simply treated and copper plating can be carried out with simple equipment under easy control.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method of copper plating a wire material. (Prior art and problems to be solved) Copper electroplating methods can be broadly classified into cyanide copper electroplating methods and copper sulfate electroplating methods in terms of industrial scale. Conventionally, copper cyanide electroplating, which has excellent adhesion and uniform electrodeposition, has been widely used as a copper plating method for materials, particularly welding wires. However, copper sulfate electroplating is much less toxic and more efficient than copper cyanide electroplating, and waste liquid treatment is easier, so its application is strongly desired. However, copper sulfate electroplating usually does not provide good quality plating because equivalent copper with poor adhesion is deposited due to the reaction of Cu''+Fe-+Cu+F'e2+ during electrodeposition. In order to prevent copper head loss, strike plating using cyanide IA electroplating has been carried out in advance. Although this cyanide copper strike plating can take advantage of the high efficiency of copper sulfate electroplating, it is toxic and Problems regarding waste liquid treatment still remain unresolved, and two completely different types of baths, a cyanide steel bath and a copper sulfate bath, are used, making equipment and bath management extremely complex. On the other hand, as a base plating method, a method was proposed in which allylthiourea was added as an I conversion inhibitor to the usual immersion displacement plating method using copper sulfate (Japanese Patent Publication No. 4329/1983). However, in the displacement plating process, even slight changes in the bath composition lead to an extreme decrease in adhesion, resulting in poor stability, and in terms of waste liquid treatment, BOD and COD are lower than additive-free baths.
The disadvantage is that it becomes difficult to deal with regulations. The present invention was made in order to solve the problems of the prior art described above, and in addition to low toxicity and high efficiency, waste liquid treatment is easy and copper plating with stable and good adhesion can be obtained. The purpose of the present invention is to provide a method for copper plating wire materials. (Means for Solving the Problem) In order to achieve the above object, the present inventors have solved the problem of toxicity and
In view of the various problems associated with the use of different types of plating baths, we recommend using electroplating baths that are basically similar but have low toxicity and are easy to dispose of as waste liquids other than copper cyanide baths. The present invention was developed as a result of intensive research to find conditions that would provide high efficiency and easy equipment and management. be. In short, the copper plating method for a wire material according to the present invention is to apply Cu S 04.5 l to a running wire material.
-120≧0.5g/lH2SO,r: 0.1~4
A copper sulfate displacement plating solution having a bath composition of 00g/lFeSO4・7H, ○≦400g/Q, or a bath composition in which CΩ""=0.01 to 100g/l is injected from a nozzle to perform base plating. After that, copper sulfate electroplating is performed. The present invention will be explained in more detail below. As mentioned above, one aspect of the present invention is to use a copper sulfate plating solution having a specific composition during base plating prior to copper sulfate electroplating (hereinafter sometimes simply referred to as "electroplating"), and furthermore, this copper sulfate plating solution The main idea is to adopt a method of ejecting from a nozzle (nozzle injection method) rather than simply using it. To do this, first, a displacement plating bath with specific components and composition is prepared as shown below. ■ Stop: If the concentration of CuSO4.5+II, O is less than 0.5 g/l, the plating deposition rate is too slow, and at an economical processing speed or time, it is difficult to prevent displacement copper deposition in subsequent electroplating. This is not preferable because the required amount of plating cannot be obtained and the adhesion after electroplating deteriorates. Therefore, the concentration of CuSO4.5H,O is 0.5g/
l or more. And J: H, SO, are components that have the effect of improving adhesion. However, if the concentration is less than 1 g/l of O, this effect is not achieved and the adhesion required for the base plating cannot be obtained. 40 again
If it exceeds 0g/12, the adhesion of the base plating will be good, but the plating deposition rate will be extremely slow and the required amount will not be obtained efficiently, resulting in poor adhesion after electroplating, and furthermore, the required amount will be reduced. The number of turns required to obtain the desired amount of water is increased, resulting in excessively large equipment, and a large amount of neutralizing agent is required for wastewater treatment, which is uneconomical. Therefore, the concentration of H2SO4 is in the range of 0.1 to 400 g/l. Immunization j9□2Lμjp-: The higher the concentration of FeSO4.7H20, the better the adhesion, but if it exceeds 400 g/l, it is inappropriate for the same reason as H and SO2. Therefore, Fe5O9・7H20
The concentration should be 400g/l or less. CV: In displacement plating baths, the higher the bath temperature, the faster the plating deposition rate increases, so the plating time required to obtain the required amount of plating Cu in the base plating is shortened, thus reducing the capacity of plating equipment. However, on the contrary, the adhesion deteriorates. In this regard, in the present invention, by injecting the displacement plating solution from the nozzle at high speed, an extremely high plating deposition rate can be obtained. However, the present inventors have conducted extensive research to find an additive that does not reduce adhesion even when the bath temperature is raised in order to further increase the plating deposition rate, and that is easy to control concentration and treat waste liquid. We obtained new findings that CQ- is effective. That is, CQ- has the function of improving adhesion even in a small amount and maintaining the high plating deposition rate obtained by increasing the bath temperature. However, if too much is added, the plating deposition rate will drop rapidly, and the effect of raising the bath temperature will be lost. Therefore, the appropriate concentration of CQ- is 0.01 to 100.
The range is ε/l. In addition, as CQ- (chlorine), NaCQ, KCQ, Ca
Cn2. MgCf12. fICQ etc. can be used. Next, the relationship between the displacement plating solution having the above bath composition and the subsequent electroplating solution will be explained. The base plating affects the quality of plating adhesion after electroplating, but in order to obtain a good base plating, the replacement plating solution should be used to suppress the copper sulfate concentration and to obtain a plating that is as M-dense as possible, as described above. Tao's H□So, and Fe5o4
- Contain 7H20. On the other hand, the electroplating solution may contain a high concentration of copper sulfate, which has high conductivity, since copper is simply electrodeposited on the base plating which is already dense and has good adhesion. Therefore, in order to obtain the most efficient plating with excellent adhesion, it is desirable that the displacement plating solution and the electroplating solution are adjusted to have the following compositions. but,
If handling two types of plating solutions is complicated, the power consumed by electroplating will increase slightly, but the displacement plating solution can be used as is. Desired weight: 1, Efushojo CuS O4.5 H2O: 0.5-150g/Q
H2So4: 1 ~ 400g/l FeSO, ・7 H□O: l ~ 400g/O
1 car "Convex and viewing lambda drainboard"1" Hime CuS○, ・5H, 0: 100-300g/RFe
5O4・7H20: ≦400g/lH, So, :
10-300g/Q Displacement plating time is determined as appropriate in relation to the plating method described below. wire diameter 0.8~5
, it is difficult to obtain the plating required to uniformly plate the surface of a wire rod of about 5 mm.On the other hand, if the plating time exceeds 10 seconds, there is no quality problem, but especially when the plating process is directly connected to one or both of the previous and previous processes. This is not preferable because the equipment length becomes too long and the occurrence of defects when plating is stopped increases. Next, the base plating method according to the present invention will be described in detail. This base plating method is a method in which a displacement plating solution having the composition shown in the following table is injected from a nozzle onto the moving wire material.
A displacement plating solution supplied under pressure by a high-pressure pump or the like is sprayed continuously at high speed through a nozzle.As a result, the solution that has completed the substitution reaction does not stay around the wire, but instead flows into a high-speed jet or The plating liquid is blown away by the jet stream, and the recesses on the wire surface are shockingly cleaned and replaced with fresh plating liquid. The cleaning and replacement effect is very large, and plating with good adhesion is completed instantly. FIG. 1 shows an example of a displacement plating apparatus used for base plating in the present invention, in which 1 is a wire running at an appropriate speed, 2
is a nozzle that injects a displacement plating solution having the above composition onto this wire, and one or more nozzles are arranged in the running direction of the running wire 1, and one or two or more nozzles are arranged at a predetermined angle in the radial direction. has been done. 3 applies high pressure (e.g., 0.5 kg/cm2) through a vibrator 4 so that the displacement plating solution 6 injected from the nozzle 2 collides with the wire surface at a necessary impact pressure of 0.05 kg/am2 or more. "that's all)
This is a pump that supplies displacement plating solution with
The plating solution 6 is circulated under the I5. Note that 7 is a nozzle for washing or washing arranged in the washing tank 8, which uses a pump 9 to spray water onto the wire 1 immediately after being plated. The injection direction from the nozzle 2 can be in various forms depending on the running direction of the running wire 1, and the angle θ of the injection direction with respect to the wire running direction can be arbitrarily determined within O°≦θ≦180°. (Figure 2), when 90° and θ≦180°, forward direction (same direction nozzle method), 0°≦θ<90°
When 0<0<180°, it can be said to be a reverse direction (counterflow nozzle system), and when 0<0<180°, it can be said to be an intersecting direction. In order to apply an effective impact force to the wire surface with the plating solution, it is best to use the plating solution in the right angle direction (0 = 90'), and the relative speed can be increased by using a counterflow nozzle method that sprays the plating solution in the opposite direction to the wire running direction. Therefore, the angle O can be appropriately selected depending on the wire properties, feeding method, etc. It goes without saying that in the forward direction, the fuel is injected with a relative speed difference from the wire traveling speed. Furthermore, one or more nozzles can be appropriately selected and arranged in the wire traveling direction, and one or two or more nozzles can be appropriately selected in the wire radial direction depending on the plating conditions such as the wire traveling speed and the predetermined plating thickness. When arranging multiple nozzles in the wire radial direction. It can be selected in consideration of the cross-sectional shape of the wire in various directions such as 2 directions and 3 directions with respect to the wire diameter, and in the case of round wire, the angle δ formed in each direction is taken as the angle δ in each direction. is about δ=180° (Figure 3), and when there are 3 pieces, it is about δ4
, δ2, δ, = 120' (Fig. 4), so that the plating liquid can efficiently hit the entire surface of the wire by arranging them at the same or almost the same angle as shown in Fig. 4. is desirable. In addition, regarding the wire running method, the above example shows a case where the wire runs straight, but FIGS. 7(a) and (b)
), in the case of a method in which a plurality of turn rollers 10 are disposed in the plating tank 5 to change the direction of the wire 1 multiple times, a plurality of turn rollers 10 are arranged in the plating tank 5 so that the plating liquid is sprayed onto the front and back surfaces of the wire. The nozzle 2 can be arranged, and in this case, the length of the plating tank 5 can be reduced. Furthermore, as shown in FIG. 8, it is also possible to run the wire 1 in a spiral pattern and spray the plating solution with the nozzle 2 at the top, bottom, etc. of the spiral trajectory. The processing length in the direction of movement can be reduced. Note that the nozzle shown in the above nozzle arrangement is an example in which the nozzle is arranged on the outside of the running wire, and can be called a jet nozzle system. A running system is also possible. That is, as shown in FIG. 5, the wire 1 is passed through the center of the pipe-shaped nozzle 2', and the plating solution 6 is injected in the opposite direction (counterflow) to the running direction of the wire to increase the relative speed. This method prevents the accumulation of iron ions and constantly supplies fresh plating solution. In addition, if one or more nozzles are provided so that the spraying direction of the plating solution is the same as the wire running direction (forward flow), the spraying direction will be in the forward direction, so there will be a relative speed difference with the wire running speed. It is best to inject it. In the case of a forward direction nozzle arrangement of such a nozzle center wire traveling method or in the case of a counterflow nozzle arrangement, the effect is smaller than that of the i-official jet nozzle method. This is because the plating solution injected from the nozzle forms a laminar flow parallel to the shear wire surface, so the agitation of the plating solution is poor, and activation of the wire surface and ion diffusion of the plating solution are small. Although it is difficult to obtain sufficient effects, it is much better than the conventional immersion plating method. In the case of the nozzle-centered wire traveling method as well, a pair of pipe-shaped nozzles 2' are arranged symmetrically and oppositely as shown in FIG.
A modified method is possible in which the wire 1 is run in the center of the nozzle and the plating liquid 6 is sprayed in intersecting directions. in this case,
The plating solution is injected at high speed from each nozzle, and at the part where the laminar region 11 of the opposing flow (downstream nozzle) and forward flow (upstream nozzle) collide, it becomes completely turbulent A (turbulent region 12), and the entire circumference of the wire surface is generated. Instantaneous replacement of the plating solution is achieved. As the ejected flows in both directions collide in this manner, the impact force activates the wire surface, and the generated turbulence increases the ion diffusion of the plating solution, resulting in high-speed and efficient plating. However, in the case of the nozzle-centered wire running method, it is necessary to provide a gap in the nozzle for the wire to pass through smoothly. is likely to intervene, so the replacement efficiency is lower than that of the jet nozzle method,
Alternatively, the plating efficiency tends to decrease due to oxidation of the wire base and deterioration of the plating solution. Since the wire runs in a narrow gap, the deposited metal copper may grow on the nozzle end and damage the wire, so this point must be kept in mind. Furthermore, depending on the nozzle arrangement, the injected plating solution may reach a long distance, resulting in a mistake 1, which may worsen the environment. Next, other points to be noted in each injection mode of the present invention will be explained. First, apply liquid to the wire hM'! Regarding the pressure, the higher the pressure, the better in order to achieve each effect of the injection described above, and a value of 0.05 kg/- or more is desirable. The higher the impact pressure, the better the plating adhesion. Depending on this impact pressure, the supply pressure of the plating solution by the pump, the abrasive flow, etc. are determined. In addition, as for the aspect of the spray width by the nozzle, as shown in Fig. 9, when spraying onto one wire 1 with one nozzle 2, the spray width (range) is narrowed as shown in (a). It is possible to hit the spray in a concentrated manner, and when spraying multiple wires 1 with one nozzle 2, the spray width (range) can be widened to hit the spray as shown in (b). In this case, the spray width can be changed depending on the shape of the outlet of the nozzle 2, if necessary. Furthermore, the linear speed of the wire is not particularly limited, but
Even if the plating bath composition is selected over a wide range of 50 to 500 m/llin, good plating can be achieved within the range of the present plating bath composition, and the plating equipment can be downsized. '! of the amount of plated Cu depending on the line speed!
JJ Seiki is the total wire length (wire length inside the plating equipment)
and effective length of plating liquid contact (spray part length O8, O
This is possible by appropriately selecting the sum of 2... (see FIG. 10). (Example) Next, an example of the present invention will be shown. Using the equipment shown in Figures 7 (a) and (b), copper sulfate displacement plating solutions with various compositions shown in Table 1 were sprayed from the nozzle to perform base plating, and then Perform copper sulfate electroplating,
A performance confirmation test was conducted. The results are also listed in Table 1. Note that 1) the treatment was performed by TICQ and pickling, and the details of the base plating conditions and copper sulfate electroplating conditions are as follows. Lower'E and 1/- Wire to be plated: Mild steel wire (wire diameter 2, 6 mm) Plating bath temperature: 30'C Injection pressure 1. kg/cm" Plating solution jet flow M: 450Q/min Total wire length: 2m (Wire length inside the device in Figure 7) Plating solution contact effective length: 0.2m (Spray part length Q□, O2・(total of..., see Figure 10) Wire running speed: 150o+/min 100o 1ofu 1
-1 Tocho CuS O4.5 H2O: 250g/QH2So
:50g/l Bath temperature: 60°C Cathode current density: 50 A/dm" Line speed: 150m/min Total wire length = 20m Also, regarding the evaluation of adhesion after copper sulfate electroplating,
Co-wound the sample wire as shown in Figure 11, and visually observe the state of plating peeling on the surface of the wound wire at a magnification of 30 times. If there is no peeling at all, mark ◎, if there are traces of peeling. Mark 0 if there is some peeling, mark Δ if there is some peeling.
Cases with a large amount of peeling were marked with an X mark and evaluated. This evaluation criterion is the same in Examples 2 and 3 below. As is clear from Table 1, No. 5 to Hal 2 are examples of the present invention, and the adhesion after electroplating is good. this is,
This is thought to be because the adhesion of the base plating is good and a sufficient film thickness is ensured to prevent displacement copper deposition during electroplating. On the other hand, Comparative Examples J Buddha 1 to Nα4, which are outside the scope of the present invention, have poor adhesion after electroplating. This is because the adhesion of the base plating is poor (Nn2), or the adhesion of the base plating is good but the above film thickness is not ensured (&1, No. 3~
Nci 4). In particular, No. 5 to Ha 8 and NQ, L of the present invention examples
O has very good adhesion after electroplating. this is. CuSO4・5H20a degree is low at less than 150g/l. This is thought to be because the adhesion of the base plating is particularly good. In addition, as electroplating conditions, CuSO4・
5H20: 10-300g/lH2So,: 10-30
0g/l bath! : 10 to 80°C Cathode current density: It has been confirmed that similar good plating can be obtained within the range of 1 to 300 A/dm2. Further, the plating CuJi obtained after electroplating is in the range of 0.2 to 0.3% by weight based on the total weight of the wire. Furthermore, thiourea compounds such as thiourea, allylthiourea, acetylthiourea, molasses, gelatin, dextrin, naphthalene disulfonic acid, glycerin, amines,
It has also been confirmed that similarly good plating can be obtained by adding various additives that contribute to suppression of field exchange or uniform electrodeposition, such as amino acids, polyacrylamide, linear carboxylic acids, and butyne diol. In order to confirm the effect of adding chlorine (CQ-) when the plating bath temperature is raised in base plating,
), (b) was used to perform base plating by spraying copper sulfate displacement plating solutions of various compositions with various plating bath temperatures and CQJ degrees from the nozzle as shown in Table 2. After that, copper sulfate electroplating was performed, and performance tests 1 to 1 were conducted. The results are also listed in Table 2. The pretreatment was carried out by I (CQ pickling), and the base plating conditions and copper sulfate electroplating conditions were the same as in Example 1. As is clear from Table 2, the amount of CQ added was 0°007
In the case of low g/l (N(11~&6)), the adhesion after electroplating tends to decrease as the plating bath temperature and temperature increase.This is thought to be due to the decrease in the adhesion of the base plating. On the other hand, when the amount of CΩ added is too high as 110 g/l (N
α16. No. 17) had poor adhesion after electroplating. This is thought to be because, although the adhesion of the base plating is good, the deposition rate drops rapidly and a film thickness sufficient to prevent displacement copper deposition during electroplating cannot be obtained. However, if the CQ-addition amount is 0.01g/l or more, 100g
When controlled to an appropriate range of /l or less (Nα7
-N(115) has very good adhesion after electroplating. This is because the adhesion of the base plating does not deteriorate even when the plating bath temperature reaches high temperatures, and the necessary film thickness is ensured. The amount of plated Cu obtained after electroplating is in the range of 0.2 to 0.4% by weight based on the total weight of the wire.

[Left below]

In order to compare the base plating according to the present invention (nozzle injection method) with the base plating by the normal immersion displacement plating method disclosed in the above-mentioned Japanese Patent Publication No. 54-4329, each base plating was carried out. After that, conduct copper sulfate electroplating,
A performance confirmation test was conducted. The results are shown in Table 3. The conditions for base plating and sulfuric acid fA electroplating conditions are as follows. Anal plated wire rod: Mild steel wire rod (wire diameter 2, 6 +nrr
rφ) Linear speed: 150 m/min Upper weir 11 drawing bath composition: CuSO4・5H20=50g/lH2SO4
=100g/l Fe SO4・7 H20=5 g/QHowever,
Allylthiourea (additive) was tested with and without addition as shown in Table 3. Bath temperature: As shown in Table 3, several different bath temperatures were tested. Plating time: 1Oscc Plating method: Inventive examples were tested using the nozzle injection method shown in Example 1, and comparative examples were tested using a normal immersion method. Aoi M 14 mki no 1” 11 Bath composition: CuSO4・5112o=250g/lH, S
04=50g/l FeS04・7H20=Og/c Bath temperature: 30°C Cathode current density: 3A/dI112 Total wire length: 300m As is clear from Table 3, at any base plating bath temperature, the present invention example The adhesion after electroplating is better than that of the comparative example. This is thought to be because although the required thickness of the base plating was secured in both the inventive example and the comparative example, the adhesiveness was better in the inventive example. The amount of plated Cu after electroplating is in the range of 0.4 to 0.5% by weight based on the total weight of the wire. In addition, in Example 1 of the present invention, since it is a new method different from the usual immersion method even with the same displacement plating, there is no need to add a displacement inhibitor. Suppression of substitution of urea-based compounds, saccharides, gelatin, dextrin, naphthalene disulfonic acid, glycerin, amines, amino acids, polyacrylamide, linear carboxylic acids, butyne diol, etc., or the density, uniformity, and gloss of plating skin. It was confirmed that similar effects can be obtained by adding various additives that contribute to properties, etc. [Margin below] As is clear from the above examples, in the base plating of the present invention, the necessary plating can be completed instantly and it is possible to obtain a wire with excellent plating adhesion. If the plating solution stays around the wire, unnecessary metal steel will grow, so to prevent this,
It is preferable to perform liquid draining or washing immediately after plating as much as possible in the process, and in particular, to obtain plating with good adhesion required for welding wire. To give an example of this, in the case of the jet nozzle system shown in FIG. 1, a cleaning tank is provided on the outlet side of the plating tank 5. By arranging one or more similar nozzles in the tank and cleaning the wire with jet water at a pressure, flow rate, etc. that suits the wire properties, the wire can be cleaned immediately after plating is completed to prevent unnecessary metal steel growth. can be prevented. In addition, it has been confirmed in experiments that a predetermined plating adhesion can be obtained by washing with water within 3 seconds after spraying the final plating solution. In addition, experiments were conducted under the following additional conditions, and it was confirmed that similar effects could be obtained within these ranges. That is, the plating solution may contain various impurities from chemicals, wires, industrial water, equipment materials, etc., but it is desirable that the amount of these impurities be 5 g/l or less. Drugs (C
Impurities from uS04, FeSO4, H2S04) include Ni, Pb, Zn, As, Mn, Ti, S
e, Hg and various phosphates and nitrates. These include ammonium compounds, sulfates, and nitrogen compounds. Impurities from the wire include wire chemical components Mn and S.
There are surface deposits such as i, AQ, Ti, Cr, Ni, and oils and fats. Impurities from industrial water include Ca, Mg,
Inorganic compounds such as silicates, sulfates, chlorides, carbonates, hydrogen carbonates, and nitrates such as Na, Fe, and Mn, and silicates, sulfates, chlorides, and nitrates of AQ, or 0
2. There are gases such as CO2 and N2. Impurities from equipment materials include those dissolved from equipment materials such as stainless steel, resin, and rubber. Further, Fe3+ in the plating solution is desirably 5Qg/l or less. If this value is exceeded, the adhesion of plating tends to deteriorate, and it may be controlled to the above value by, for example, flowing an atmosphere for preventing oxidation. The analysis method for Fe3+ is JIS M
8853 0-phenanthroline by spectrophotometry. It is desirable that the plating solution has a specific gravity of 1.05 to 1.35 (20°C), a viscosity of 1.30 to 3.50 cp (20'C), and a pH of 1°5 or less (20°C). Yet again. As a wire, the tensile strength (TS) is 30~
300 kgf / ml112, or the decarburization depth 1 grain boundary oxidation depth of the wire before plating is 0.50 + n
A similar effect can be obtained even when applied to objects with a diameter of m or less. In addition, the spray part length Q (the length of the wire that is directly hit by the spray liquid) and the non-spray part length L (the wire length that is not directly hit by the spray but is attached or immersed in the liquid) are calculated using the following formula: % It is desirable to have a relationship that satisfies the following. Although L+Q can be made as long as desired depending on the relationship between the amount of plating and the linear speed, the same effect can be obtained as long as L+Q≦200 m. In addition, although the above explanation mainly takes as an example the case of displacement copper plating for welding wire, it is not limited to displacement copper plating.
Similar effects can be obtained in displacement tin plating or in the case of depositing two or more metals, such as those containing both copper sulfate and tin sulfate. Furthermore, it goes without saying that welding wires may be not only solid wires but also flux-cored wires, and are not limited to welding wires, but also bead wires or copper coated wires such as furniture springs and cardboard fasteners. It goes without saying that it can be applied to wire materials for various uses such as metal fittings, etc., and therefore, it can be applied to various shapes (circular, band-shaped, square, etc., wires, hoops, pipes, etc.) and dimensions (0.2~ 6゜4mmφ), it can also be applied to wire material. Examples of materials include JIS Z 3312 (solid wire for mild steel and high tensile strength steel MAG welding), 3351 (
Submerged arc welding wire for carbon steel and low alloy steel)
, 331G (steel rod and wire for TIG welding of mild steel and low alloy steel), 3317 (MAG welding solid wire for molybdenum steel and chromium molybdenum steel), JIS G 3
502 (piano wire rod), 3505 (mild steel wire rod), 350
6 (hard steel wire rod), etc. (Effects of the Invention) As described in detail above, according to the present invention, base plating is performed by spraying IiA acid copper plating solution of a specific composition onto a running wire material from a nozzle, and then copper sulfate electroplating is performed. By implementing this, the following advantages can be obtained. (It is far less toxic than the D-cyanide copper bath, and waste liquid treatment is easier.) In zero-base plating, the pressure of the high-speed jet or jet of the plating solution sprayed onto the running wire material completely and instantaneously. Since displacement plating is performed, plating with excellent adhesion and uniform thickness can be obtained in a short time.It is also more efficient than a copper cyanide bath, and requires no rectifier, which simplifies equipment.■ If the base plating bath composition is the same as the electroplating bath composition, it will be extremely simple in terms of equipment and management, and even if the bath compositions are different, the two are basically similar baths, so
Both equipment and management are simpler than in the case of copper cyanide baths. The quality of the zero-base plating is different from displacement plating by the normal dipping method or the dipping method with the addition of a displacement inhibitor.The adhesion and film density are comparable to those of cyanide copper strike plating, and the quality of the plating is comparable to that of copper cyanide strike plating. Even in copper sulfate electroplating, C
The substitution reaction of u”+Fe−+Cu+Fe”+ can be prevented,
Overall, good plating with good adhesion and uniform electrodeposition can be obtained.

[Brief explanation of the drawing]

Fig. 1 is an explanatory diagram showing an example of a plating apparatus for carrying out the jet nozzle method, which is one aspect of base plating in the present invention, and Fig. 2 shows the angle θ between the jet direction from the nozzle and the wire running direction. Explanatory diagram. FIG. 3 and FIG. 4 are explanatory diagrams showing the angle δ formed by the injection direction when there are two or three nozzles. FIGS. 5 and 6 are explanatory diagrams showing nozzles and their arrangement for a nozzle-centered wire running system, which is one embodiment of base plating in the present invention. FIGS. 7(a) and 7(b) are diagrams showing examples of nozzle arrangement in the case of wire running using turn rollers, (a) is a plan view;
(b) is a side view, Figure 8 is an explanatory diagram showing an example of nozzle arrangement when the wire is run in a spiral shape, Figure 9 is a diagram showing the spray range from the nozzle, and (a) is a narrow width diagram. (b) shows the case of wide width. FIG. 10 is a diagram illustrating the length of a portion of the spray, and FIG. 11 is an explanatory diagram showing the state of wire winding used for determining plating adhesion. 1... Line material (wire), 2... Jet nozzle,
2'... Pipe-shaped nozzle, 3.9... Pump, 4.
... Pipe, 5... Plating tank, 6... Plating solution, 7
...Washing jet nozzle, 8...Washing tank, 10.
... Turn roller, 11... Laminar region, 12... Turbulent region. Figure 6

Claims (2)

[Claims] (1) A method for copper plating a wire material, which comprises spraying a copper sulfate plating solution having the following composition from a nozzle onto a running wire material to perform base plating, and then electroplating the wire material with copper sulfate. CuSO_4・5H_2O≧0.5g/l H_2SO_4:0.1-400g/l FeSO_4・7H_2O≦400g/l (2) A method for copper plating a wire material, which comprises spraying a copper sulfate plating solution having the following composition from a nozzle onto a running wire material to perform base plating, and then electroplating the wire material with copper sulfate. CuSO_4・5H_2O≧0.5g/l H_2SO_4: 0.1 to 400g/l FeSO_4・7H_2O≦400g/l Cl^-: 0.01 to 100g/l