KR20160018612A - method for wet electroplating - Google Patents

Abstract

The present technology, in an electroplating process of performing all nickel strike plating, relates to a technology for solving a problem that a nickel strike plating grows along 100 direction preferably, by a nickel strike correction plating process. By performing the nickel strike correction plating shortly after the nickel strike plating, a wet electroplating method of the present invention can solve appearance fault due to rolling fault considerably and also can solve a metal substrate surface planarization technology by the wet plating process without depending on the rolling, in technology development of wide width (1m) steel material (STS/Plated steel sheet) for a flexible thin film solar cell, which is a core material for solar light utilization technology. And, the wet electroplating method of the present invention does not need to use polish particularly, and can obtain a beautiful white plated layer regardless of not using the polish, and has less difference between a high current and a low current, and can facilitate long time keeping by suppressing surface oxidation with good solderability.

Description

[0001] The present invention relates to a method for wet electroplating,

The present invention relates to a correction plating process of nickel strike plating, which is widely used for undercoating of electroplating.

In general, the wet plating process can be divided into a reel-to-reel, a roll-to-roll, a barrel, and a rack.

These plating processes are variously plated before electroplating, depending on the type of material.

For example, chemical nickel plating, chemical copper plating, blue dyeing strike, nickel strike, and the like. Among them, the notched plating named strike is a base plating using electricity.

There are about four types of Ni strike plating as shown in Table 1.

Composition of various nickel strike plating process division Sulfamates Nickel Strike Nickel Strike Chloride Improved Nickel Strike Chloride Sulfuric acid Ni Strike Furtherance Nickel sulfamate solution: 42% Nickel chloride: 120 to 240 g / l Nickel sulfate: 112 g / l Nickel sulfate: 300 g / l Boric acid: 30 g / l Hydrochloric acid: 62 to 125 ml / l Nickel chloride: 112 g / l Nickel chloride: 60 g / l Sulfamic acid: 20 g / l Boric acid: 15 g / l Boric acid: 45 g / l Hydrochloric acid: 1.2% Hydrochloric acid: 10% carrier: 1% (optional) work
Condition Temperature 27 ~ 38 20-25 20-25 60 pH 1.5 max - - 3.5 electric current 1 to 10 ASD 1 to 10 ASD 2 to 7.5 ASD 2 to 4 ASD

Nickel strike plating is the most frequently used. The purpose of this nickel strike plating was to secure the adhesion with the material with a very short plating time and a thin thickness. Among them, nickel chloride strike plating is the most frequently used.

In addition to this, a variety of undergold platings have been developed to meet various needs such as improving the adhesion between the plating material and the plating layer to a thin thickness, securing the conductivity.

For example, in the case of plastic materials, palladium catalyzed treatment is performed to impart conductivity, followed by chemical nickel (electroless nickel) plating to ensure conductivity, chemical copper (electroless copper) plating to ensure conductivity, Various electroplating processes such as plating can be performed.

In the case of materials such as phosphor bronze, titanium copper, copper rods, brass, and stainless steel, since the material is electrically conductive, nickel chloride strike plating or nickel sulfide nitrate plating is performed after the etching process to secure adhesion between the material and the plating layer.

Due to the nature of the material, zinc is tinned copper plating after zinc plating treatment to ensure adhesion, and zinc, tin, alloys thereof, and alloys of iron and iron are highly oxidizable in the plating solution. (Rust generation) in the plating solution during plating is prevented, and adhesion is ensured.

In case of brass material, all of the copper plating or nickel strike is selectively used depending on the amount of zinc contained in the alloy.

The characteristics of these base platings are very thin, and after proper base plating according to various materials, most plating is performed to impart leveling to the surface of the base material.

For example,

Metal material: nickel strike plating - copper sulfate plating - nickel plating

Plastic material: Chemical nickel plating - Copper copper plating - Nickel plating

Plastic material: Chemical copper plating - Copper copper plating - Nickel plating

Metal material: Blue dyeing strike - Copper sulfate plating - Nickel plating

.

This is because copper plating is a metal with a lot of copper sulfate plating to give the leveling, but the surface is smoothed and a relatively easy-to-polish surface can be obtained.

In addition, there is a case where the polishing agent is turned over to the nickel plating to catch the surface leveling. However, it is not recommended because there are many problems in reliability such as discoloration resistance, glossiness and solderability.

Also, in the case of copper sulfate plating, since the thermal conductivity and the electric conductivity are different from the nickel plating layer, it causes a lot of defects due to the thermal expansion coefficient different from nickel in the thermal shock test or the constant temperature and humidity test, which is the reliability test item by the thermal conductivity, In some tests, the copper of the lower limb melts, causing a blue-green defect on the surface.

The biggest problem is that the plating product becomes unnecessarily thick.

For this reason, in the plating requiring high reliability, a process of eliminating the copper sulfate plating and immediately performing nickel plating has been mainly developed. In electroplating such as plating of electronic parts and plating of electronic parts, most of the materials are phosphor bronze, Copper alloys such as copper, copper, SUS, etc., and stainless steel have been prepared for thermal shock, and in this plating, nickel sulfate plating has been carried out without eliminating weak copper sulfate plating for thermal shock and salt spray.

For example,

Nickel Strike - Nickel Plating

Cheonghwa Dong strike - Nickel plating

Blue streak strike - Nickel strike - Nickel plating

.

In this case, there was an advantage in the reliability test such as the thermal shock test or the salt spray test. However, due to the lack of leveling, which is an advantage of the copper sulfate plating, the rolling roll marks or the fine scratches on the surface occurred during the material processing could not be removed, Lt; / RTI >

In particular, the rolling roll marks that occurred during processing were not easily erased.

That is, when the plating including the copper sulfate plating process is performed, the surface leveling of the surface of the plated product is improved, but the thermal shock test due to the different thermal conductivity of nickel and copper or the salt spray test And an unnecessary thickness of at least 5 microns to 15 microns was required for leveling. Further plating was required for plating for 10 minutes or more. In the case of not plating copper sulfate, rolling roll marks, A lot of appearance defects due to minute scratches were generated.

In order to solve this problem, in case of performing nickel plating, the main polishing agent is added by 15 times to 20 times as much as the standard bath bath, but in this case, the color of the plating surface becomes dark and dark yellow, It caused problems such as the problem to be solved and the problem of not being well sold.

The plating which is used in the pretreatment process for ensuring the reliability such as blue lightning strike, nickel strike, chemical nickel plating, and chemical copper plating, which are used for undercoating, is the adhesion with the material to be plated. After this strike plating process, There is a problem in that it takes too much time in the process of securing the plating layer and the problem of raising the thickness of the plating unnecessarily and the consumption of the polishing agent and the metal powder due to the increase.

The present invention is intended to solve various problems between nickel strike plating and nickel plating in various underlying platings.

On the other hand, in the development of a wide-width (1 m) steel substrate (STS / plated steel sheet) substrate for flexible thin film solar cells, a nickel chloride strike plating is performed through a pretreatment process, nickel plating is performed, To prepare a steel sheet for a flexible thin film solar cell.

In case of STS with excellent corrosion resistance, it is virtually impossible to secure adhesion when nickel strike plating is not performed.

At this time, the STS used is a 1 m-wide width, 100 탆 thick, and is a stainless steel plate. The roughness of the surface is defined as Ra? 0.03 占 퐉 by the planarization technique of the surface, and the planarization technique of the metal substrate depends mainly on the rolling method .

However, STS 0.1 mm (100 탆) was difficult to obtain a desired surface quality because the rolled state was uneven.

In the production of wide-width (1 m) steel material (STS / coated steel sheet for flexible thin-film solar cells), it is important to reduce the unnecessary thickness and secure a flat appearance in a thin rolled STS.

(Patent Document 1) KR10-052481 B1, a process for forming a high-adhesion plating layer on a zirconium and zirconium alloy material

(Patent Document 2) KR10-1227059 B1, a plating method of a zirconium alloy plating and a titanium alloy plating, and a plating solution

(Patent Document 3) KR10-1229500 B1, Titanium electroplating solution and plating method

Therefore, it is essential to develop a plating process capable of securing an excellent surface quality with a minimum thickness to the material to be plated.

An object of the present invention is to provide a method for easily obtaining a fine flat plating layer in a short time by introducing a nickel strike correction plating process which is a new plating process for adjusting the growth direction of a nickel chloride strike plating layer in electroplating for nickel strike plating.

Another object of the present invention is to remove nicks and nickel plating defects due to rolling roll marks of a plate material and a plate material through nickel strike correction plating, which is a new plating process for adjusting the growth direction of a nickel strike plating layer .

It is a further object of the present invention to provide a method of manufacturing a nickel strike plating method for plating a sheet material and a rolled sheet material in a short period of time by means of a Ni strike correction plating process which is a new plating process for adjusting the growth direction of a plating layer in nickel- And it is intended to remove defects such as scratches and nickel plating.

Since the growth direction of nickel strike plating used for conventional plating is preferentially oriented in the 100 direction, it is possible to remove fine scratches and rolling roll marks on the surface of the plating material in the step of directly performing nickel plating after nickel strike plating However, due to the present invention, by introducing the nickel strike correction plating process, the growth direction formed in the thin plating thickness of the nickel strike plating layer is changed into the non-oriented orientation fine fine flat deposition, thereby preventing defective plating due to fine scratches, In addition to the leveler, it is not necessary to use a polishing agent, and it is possible to eliminate the defective phenomenon even in the case of a thin nickel thickness due to poor rolling due to rolling defect in plate plating.

1 is a model of a conjoint complexing agent of Korean Patent Application No. 10-2012-0088709.
2 is a photograph of the result of Comparative Example 1. Fig.
3 is a photograph of the result of Example 1. Fig.
4 is a photograph of the result of Comparative Example 17;
5 is a photograph of the result of Example 17. Fig.
6 is a photograph of the result of Example 20. Fig.

Patent patents for forming a high-adhesion plating layer on zirconium and zirconium alloy materials show that, unlike the general plating process, the nickel-chromium chloride strike plating process and the blue- It is a patent that secures adhesion between high material and plating layer by using both strike plating process.

The present invention also has a nickel strike plating process and a glossy nickel plating process after the nickel chloride (wood nickel) strike plating process, so that the invention is easy to handle as the invention similar to the present invention.

However, the nickel strike plating process after the nickel chloride strike plating process in the process of the registered patent publication No. 10-0552481 is similar to the nickel strike correction plating process of the present invention, and has a plating time of 10 to 60 minutes The bath nickel electroplating process does not have the same effect as the present invention.

The inventors of the present invention have found that the use of a coupling type complexing agent and a conductive salt used in the process of developing a plating method for a zirconium alloy plating and a titanium alloy plating and a plating solution of Korea Patent Application No. 10-2012-0088709, It is possible to compensate for the disadvantages of the plating layer growth, thus leading to the present invention.

FIG. 1 is a schematic view of the coupling complexing agent used in the patent, and it can be seen that various combinations of nickel, cobalt, titanium, and zirconium plating and alloy plating can be realized.

In the case of correcting Ni strike plating with nickel plating solution, cobalt plating solution or nickel-cobalt alloy plating solution added with citric acid ion, which is a coupling complexing agent, and ammonium ion used as a conductive salt, it is necessary to compensate the plating weakness of nickel plating layer in a short time, It is possible to realize a fine and flat plating.

Namely, the nickel strike platings shown in Table 1, such as the conventional nickel chloride strike, the sulfamic acid nickel strike, the improved nickel chloride strike, and the nickel sulfate strike, play a role of securing the adhesion between the plating material and the plating layer with a very thin thickness. The growth direction of the plating layer is preferentially oriented in the 100 direction and grows constantly.

The present invention has led to the invention by knowing that this disadvantage can be achieved by turning the alignment direction in a short time and forming non-oriented, non-directional micro-flat precipitation into citrate ion and ammonium ion.

This could easily be done in a very short time of 1 to 4 seconds since the plating layer of various nickel strike is very thin.

The present invention has been accomplished on the basis of the fact that after the plating layer is finely adjusted, the surface appearance once adjusted is maintained well even if the plating is carried out with either sulfamate nickel plating or watt nickel plating.

That is, although the nickel strike plating is a base plating which is plated to ensure reliability, particularly adhesion, since the plating thickness is a thin layer in the unit of Angstrong, if the growth direction of the plating layer is adjusted at this stage, a fine flat plating layer can easily be obtained The present invention has been accomplished.

In addition, if the nickel strike correction amount is added to the amount of titanium ion in a small amount, the plating solution can be used as a decomposition preventing agent, thereby extending the service life of the plating solution.

However, zirconium can not be used due to the phenomenon of eliminating all of the characteristics of the present invention if a very small amount of zirconium is introduced.

Therefore, a plating process for performing electroplating after nickel chloride strike plating, which is a conventional plating procedure, is improved to newly introduce a new plating process for performing nickel strike correction plating after nickel strike plating, and thereafter plating When the process is changed, defective appearance of various electronic parts and decorative plating can be prevented in a short time, and a beautiful appearance can be easily obtained.

Hereinafter, the present invention will be described by way of examples.

[Comparative Examples 1 to 16] Nickel-nickel strike plating of phosphorus-doped copper → Watt nickel plating

Plating Material and Method: Phosphor bronze 0.1mm thick plate electroplating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.0 VOLT 10 seconds

Watt nickel plating Amount Composition: Nickel sulfate 300g / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, Wetting agent 1ml / L

Plating conditions and time: pH 4.5, temperature 55, 7 volts 3 min.

Plating results:

Under the above conditions, the problems of the prior art were identified through 16 comparative examples from the use of the polish remover to the use of 20 ml / L, 20 times the standard bath temperature.

Change of plating surface with amount of main polishing agent division Nickel chloride
strike Watt nickel electroplating (180 seconds) Plating result Voltage (V) Time (S) Leveler
(ml / L) Polish
(ml / L) Plating color Exterior Rolling roll
Remove Mark Comparative Example 1 5 10 10.0 0.0 White Matte X Comparative Example 2 5 10 10.0 0.2 Off-white Reflection X Comparative Example 3 5 10 10.0 0.4 Off-white Reflection X Comparative Example 4 5 10 10.0 0.6 yellow Bright X Comparative Example 5 5 10 10.0 0.8 yellow Bright X Comparative Example 6 5 10 10.0 1.0   yellow Bright X Comparative Example 7 5 10 10.0 2.0 Dark yellow Bright X Comparative Example 8 5 10 10.0 4.0 Dark yellow Bright X Comparative Example 9 5 10 10.0 6.0 Dark yellow Bright X Comparative Example 10 5 10 10.0 8.0 Dark yellow Bright X Comparative Example 11 5 10 10.0 10.0 Dark yellow Bright X Comparative Example 12 5 10 10.0 12.0 Dark yellow Bright X Comparative Example 13 5 10 10.0 14.0 Dark yellow Bright X Comparative Example 14 5 10 10.0 16.0 Dark yellow Bright ○ Comparative Example 15 5 10 10.0 18.0 Dark yellow Bright ○ Comparative Example 16 5 10 10.0 20.0 Dark yellow Bright ◎

Rolling roll mark removal: X - bad, ○ - good, ◎ - very good

The standard dry bath mass of the main polish is 1 ml / L. The main polish was overturned 16 times to 20 times to dry the plating solution, but the rolling roll marks produced when the plate was made could be removed to some extent.

However, the color of the plating surface gradually changed to dark yellow due to the effect of 1.4 butene diol and the like contained in the brightener.

When the polish of Comparative Example 1 is not used, the surface is in a non-glossy form and weak in the fingerprint, and the glossiness of the high current portion and the low current portion is different and the merchantability is remarkably deteriorated.

A photograph of the result of Comparative Example 1 is shown in Fig.

In the test of Comparative Example 1, the unused portion of the glossing agent in the nickel plating composition liquid was added to and increased in the glossing agent, and as a result of checking up to Comparative Example 16, the surface was smoothed when the glossing agent was added at a rate of 1 / L or more, And the color of the surface of the plating became yellow to white. This is because the main component of the brightener is 1.4. Butene diol is released between the plating layers, thereby promoting the corrosion of the plating layer and deteriorating the solderability. It causes surface oxidation.

[Examples 1 to 4] Nickel strike plating of phosphor bronze material → nickel strike correction plating → electric watt nickel plating: nickel strike correction The surface observation according to the plating time change of the plating process

Plating Material and Method: Phosphor bronze plate electroplating ..

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.0 VOLT 10 seconds,

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Citric acid 50g / L, Ammonium chloride 100g / L

Plating conditions: pH 4.0 (adjusted with ammonia and hydrochloric acid), temperature 40, 5.0 VOLT

Watt nickel plating Amount Composition: Nickel sulfate 300g / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, No polishing agent

Plating conditions and time: pH 4.5, temperature 55, 7 volts 3 min.

Plating Result: It was realized in a semi-transparent form with a beautiful surface and excellent gloss and uniform gloss was obtained without using a separate polish agent

Nickel Strike Correction Plating Process Time Result division Nickel chloride
strike Nickel (S / T)
Calibrated plating Watt nickel
Electroplating (180 seconds) Plating result Voltage
(V) time
(S) Voltage
(V) time
(S) Leveler
(ml / L) Main polish
(ml / L) Plated
color Exterior Rolling roll
Remove Mark Example 1 5 10 5 4 10.0 0.0 White Reflection ◎ Example 2 5 10 5 3 10.0 0.0 White Reflection ◎ Example 3 5 10 5 2 10.0 0.0 White Reflection ◎ Example 4 5 10 5 One 10.0 0.0 White Reflection ◎

Rolling roll mark removal: X - bad, ○ - good, ◎ - very good

In particular, even a short 1 second Ni strike correction plating process was able to completely remove the rolling rolls and secure a smooth surface even if the main polishing agent of the next process, the Watt Ni electroplating process, was not used at all.

The plating surface results of Example 1 are shown in Fig.

In this test, a glossy white plated layer was obtained in the nickel plating composition even without the use of a brightener, and all of the rolling rolls were disappeared, and the color of the plating was not a yellowish white gloss .

This phenomenon is a good phenomenon that is caused by not using 1.4-butene diol, which is the main component of the brightener, and it is not necessary to use the brightener because it improves the solderability and the oxidative deterioration of the plating surface is improved more than twice.

In other words, by controlling the growth direction of the nickel strike plating finely by the nickel strike correction plating process, it is possible to secure a beautiful appearance without using the polishing agent in the post-process watt nickel electroplating process.

Therefore, in the prior art, a plated layer without a gloss agent can not be obtained without plating, but a pure nickel plating layer is obtained as much as possible from the prior art which does not have a good surface oxidation even if a polishing agent is not used.

[Examples 5 to 16] Nickel strike plating of phosphorous-bronze material → nickel strike correction plating → electro-nickel plating In the electroplated nickel plating process,

Plating Materials and Methods: Phosphor bronze plate plate electroplating.

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.0 VOLT 10 seconds

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Citric acid 50g / L, Ammonium chloride 100g / L

Plating conditions: pH 4.0 (adjusted with ammonia and hydrochloric acid), temperature 40 ° C, 5.0VOLT 1 second

Watt nickel plating Amount Composition: Nickel sulfate 300g / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, No polishing agent

Plating conditions and time: pH 4.5, temperature 55, 7 volts 10 seconds to 180 seconds.

Result of Ni plating process time change after nickel strike correction plating division Nickel chloride
strike Nickel (S / T)
Calibrated plating Watt nickel
Electroplating Plating result Voltage
(V) time
(S) Voltage
(V) time
(S) time
(S) Leveler
(ml / L) Main polish
(ml / L) Plated
color Exterior Removing rolled roll marks Example 5 5 10 5 One 10 10.0 0.0 White Reflection ○ Example 6 5 10 5 One 20 10.0 0.0 White Reflection ◎ Example 7 5 10 5 One 30 10.0 0.0 White Reflection ◎ Example 8 5 10 5 One 40 10.0 0.0 White Reflection ◎ Example 9 5 10 5 One 50 10.0 0.0 White Reflection ◎ Example 10 5 10 5 One 60 10.0 0.0 White Reflection ◎ Example 11 5 10 5 One 80 10.0 0.0 White Reflection ◎ Example 12 5 10 5 One 100 10.0 0.0 White Reflection ◎ Example 13 5 10 5 One 120 10.0 0.0 White Reflection ◎ Example 14 5 10 5 One 140 10.0 0.0 White Reflection ◎ Example 15 5 10 5 One 160 10.0 0.0 White Reflection ◎ Example 16 5 10 5 One 180 10.0 0.0 White Reflection ◎

Rolling roll mark removal: X - bad, ○ - good, ◎ - very good

As shown in the above embodiment, when the nickel chloride strike correction plating process is introduced, it is possible to ensure a beautiful appearance even if the nickel plating time is remarkably short.

In particular, the rolling roll marks formed at the time of material rolling were almost completely removed even after plating for only 10 seconds or more, thereby significantly reducing surface defects.

[Comparative Example 17] SUS 304 nickel chloride plating → electrical nickel plating

Plating Material and method: SUS 304 0.1mm plate ROLL TO ROLL Continuous plating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating conditions and time: Temperature Normal temperature, 5.5VOLT 10 seconds

Nickel plating Amount Composition: Sulfamine nickel 400ml / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, Brightener 0.3ml / L

Plating conditions and time: pH 4.5, temperature 55, 7 volts 4 min.

Plating Result: Although the surface was realized in a semi-transparent form, the rolling roll marks formed on rolling occurred as it was on the plated layer, resulting in appearance failure. The results are shown in Fig.

The unprinted rolling roll marks are clear in the drawing.

The color of the plated layer was light and off-white.

[Example 17] Nickel strike plating of SUS 304 → nickel strike correction plating → electric nickel plating.

Plating Material and method: SUS 304 0.1mm plate electroplating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.5 VOLT 10 seconds,

Nickel Strike Calibration Chart Amount Composition: Nickel chloride 400g / L, Citric acid 50g / L

Plating conditions and time: pH 4.0 (adjusted with ammonia, hydrochloric acid), temperature 40 ° C, 5.0VOLT 4 seconds

Watt nickel plating Amount Composition: Sulfamine nickel 400ml / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L

Plating conditions and time: pH 4.5, temperature 55 캜, 7 volts 4 min.

Plating Result: The surface was realized in a beautiful semi-transparent form, and the defects such as rolling rolls disappeared, but the plating layer was not formed at the high current rim area and the ballistic phenomenon appeared. The results are shown in Fig.

In this experiment, it is more preferable not to use a polishing agent to coat the surface with white.

As a result, a whitish white product as in Examples 1 to 16 can be obtained without using a polishing agent. The more the use of the polishing agent is, the better the solderability, the long-term storage property, and the corrosion resistance.

Example 18 Nickel strike plating of SUS 304 → nickel strike correction plating → electro nickel plating.

Plating Material and method: SUS 304 0.1mm plate electroplating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.5VOLT 10 seconds,

Nickel Strike Calibration Chart Amount Composition: Nickel chloride 400g / L, Ammonium chloride 100g / L

Plating conditions and time: pH 4.0 (adjusted with ammonia, hydrochloric acid), temperature 40 ° C, 5.0VOLT 4 seconds

Nickel Coating Composition: Sulfamine nickel 400 ml / L, Nickel chloride 20 g / L Boric acid 40 g / L, Leveler 10 ml / L, Brightener 0.3 ml / L (Brightener was added to keep the color of the plating layer in the prior art .)

Plating conditions and time: pH 4.5, temperature 55 캜, 7 volts 4 min.

Plating Result: The surface was realized in a beautiful semi-transparent form, the defects such as the rolling marks disappeared and the high current region ballast gold disappeared.

It is more preferable not to use a polishing agent for plating the plating layer with a beautiful white color. That is, the present invention can provide a plated layer without using a polishing agent.

However, the nickel strike correction also caused a problem in that the decomposition rate of ammonium chloride in the solution was so fast that a substantial amount had to be replenished more than twice a day, and it was difficult to maintain the plating solution.

[Example 19] Nickel strike plating of SUS 304 → nickel strike correction plating → electrical nickel plating.

Plating Material and method: SUS 304 0.1mm plate electroplating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.5VOLT 10 seconds,

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Citric acid 50g, Ammonium chloride 100g / L

Plating conditions and time: pH 4.0 (adjusted with ammonia, hydrochloric acid), temperature 40 ° C, 5.0VOLT 4 seconds

Nickel plating Amount Composition: Sulfamine nickel 400ml / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L

Plating conditions and time: pH 4.5, temperature 55 캜, 7 volts 4 min.

Plating Result: The surface was realized in a beautiful semi-transparent form, the defects such as the rolling marks disappeared and the high current region ballast gold disappeared. In addition, the liquid stability was excellent enough to supplement the replenishment amount of ammonium chloride once or twice a day.

[Example 20] Nickel strike plating of SUS 304 → nickel strike correction plating → electrical nickel plating.

Plating Material and method: SUS 304 0.1mm plate electroplating

Nickel chloride plating Amount Composition: Nickel chloride 300g / L, industrial hydrochloric acid 100ml / L

Plating Conditions and Time: Temperature Normal temperature, 5.5VOLT 10 seconds,

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Titanium sulfate (TiOSO ₄ 2H ₂ O) 50g, Citric acid 50g, Ammonium chloride 100g / L

Plating conditions and time: pH 4.0 (adjusted with ammonia and hydrochloric acid), temperature 40 ° C, 5.0VOLT 10 seconds

* Nickel plating Amount Composition: Sulfamine nickel 400ml / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L

* Plating conditions and time: pH 4.5, temperature 55 ° C, 7Volt 4 minutes.

Plating Result: The surface was realized in a beautiful semi-transparent form, the defects such as the rolling marks disappeared and the high current region ballast gold disappeared. Titanium sulfate and citric acid were reacted in a separate vessel at a high temperature of 60 to 90 ° C or higher to synthesize a clear ionic solution and then added.

It was also possible to maintain the plating solution even if the replenishment amount of ammonium chloride was supplemented only about once a week. The results are shown in Fig.

It was judged to slow the decomposition rate of citric acid when it was in the form bound to the added trace amount of citric acid.

Cobalt ions may be added, but it is difficult to expect cobalt ions to act like titanium, but nickel and alloys provide a slightly harder layer.

[Example 21] Nickel strike plating of sulfamic acid in phosphor bronze → plating of nickel strike correction → Appearance observation in electric nickel plating

Plating Materials and Methods: Phosphor bronze plate plate electroplating.

Sulfamic acid Nickel strike plating solution Composition: Nickel sulfamate solution 400 ml / L, industrial hydrochloric acid 20 ml / L, sulfamic acid 20 g / L, boric acid 30 g / L, pH 1.5

Plating Conditions and Time: Temperature Normal temperature, 5.0 VOLT 10 seconds,

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Titanium sulfate (TiOSO ₄ 2H ₂ O) 50g, Citric acid 50g, Ammonium chloride 100g / L

Plating conditions: pH 4.0 (adjusted with ammonia and hydrochloric acid), temperature 40 ° C, 5.0VOLT 2 seconds

Watt nickel plating Amount Composition: Nickel sulfate 300g / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, No polishing agent

Plating conditions and time: pH 4.5, temperature 55 ° C, 7 volts 180 sec.

Plating Result: The growth direction of the plated layer of the sulfamic acid nickel strike was also firstly cultured in the 100 direction, and it could be confirmed that the Ni strike correction plating process can make the micro-flatness in the non-directional culture.

The phosphor bronze material did not cause bad adhesion even if nickel chloride strike was not used.

[Example 22] Nickel strike plating of phosphorus-doped nickel sulfate → nickel strike correction plating → Appearance observation in electric nickel plating

Plating Materials and Methods: Phosphor bronze plate plate electroplating.

Nickel strike plating solution Composition: Nickel sulfate 300g / L, Nickel chloride 60g / L, Boric acid 45g / L, Leveler 10ml / L, pH 3.5

Plating condition and time: Temperature 60 캜, 5.0 VOLT 10 seconds,

Nickel Strike Correction Diagram Composition: Nickel chloride 400g / L, Titanium sulfate (TiOSO ₄ 2H ₂ O) 50g, Citric acid 50g, Ammonium chloride 100g / L

Plating conditions: pH 4.0 (adjusted with ammonia and hydrochloric acid), temperature 40 ° C, 5.0VOLT 2 seconds

Watt nickel plating Amount Composition: Nickel sulfate 300g / L, Nickel chloride 20g / L Boric acid 40g / L, Leveler 10ml / L, No polishing agent

Plating conditions and time: pH 4.5, temperature 55 ° C, 7 volts 180 sec.

Plating Result: The growth direction of the plated layer of the nickel sulfate strike was also firstly cultured in the 100 direction, and it was confirmed that the nickel strike correction plating process can make the non-directionally non-cultured micro flatness.

Among the above Examples 1 to 22, the citrate ion used in the nickel strike correction plating process can be obtained by dissolving citric acid, sodium citrate, potassium citrate and ammonium citrate, and the ammonium ion is obtained by dissolving ammonium chloride, ammonium sulfate and ammonium nitrate Can be obtained.

In addition, as a method of using titanium ion as an additive for slowing the decomposition rate of the plating solution in the nickel strike correction plating process, any one of titanium sulfate, titanium tetrachloride and titanyl sulfate should be reacted with citrate ion.

At this time, it is more preferable to dissolve titanium sulfate, titanium tetrachloride and titanyl sulfate in a solution in which citric acid or ammonium citrate is dissolved by dissolving titanium or the like in the solution containing no sodium or potassium.

After the nickel strike plating process and the nickel strike correction plating process are performed as described above, conventional wet electroplating is used for the main plating.

Typical wet electroplating solutions for such a main plating are Zn, Cr, Fe, In, Cd, Zr, Ti, Co, Ni, Sn, Pb, Bi, Cu, Pd, Ag, Pt, , And V. The term " wet electroplating solution "

As described above, in the prior art, it is difficult to obtain a beautiful appearance of a plated layer without using a polishing agent, and even if a plated layer is obtained by using a diazo polishing agent, the polishing agent component is excessively vacated and deteriorated in performance such as solderability and corrosion resistance It is difficult to solve the problem. However, it is possible to supplement the growth direction of the nickel strike plating by making the growth direction to the non-oriented orientation through the Ni strike correction plating process before the thickness becomes thicker, The surface thus calibrated was then retained even after another electroplating thereon.

In particular, a beautiful plating layer can be obtained even if all of the brightener containing 1.4-butynediol, which is a major component of the brightener that has been caused by the nickel plating layer, is used, and the maintenance of the solderability and the prevention of oxidation The reliability can be further improved.

Accordingly, since the nickel strike correction plating is performed after nickel strike plating, not only the appearance defect due to the rolling defect can be largely solved, but also a large (1 m) steel material for flexible thin film solar cells (STS / coated steel sheet) substrate, the technique of flattening the surface of the metal substrate can be solved simply by a wet plating process without depending on rolling.

However, the nickel strike plating process of the present invention in which the thick-thickness plating is already performed instead of the nickel strike plating is very difficult to easily adjust the growth direction of the plating layer, and only the strike plating layer of a very thin ingot- Can be easily adjusted by adjusting the growth direction.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Claims (5)

In the electroplating process for performing nickel chloride strike plating,
1) plating the plated body with nickel chloride strike;
2) After the nickel chloride strike plating, the nickel chloride strike plating layer is uniformly filled in accordance with the removal of the nickel chloride strike plating layer and the plated nickel chloride strike plating layer according to the scratch shape of the plated body, and the growth direction of the nickel chloride strike plating layer is defined as a non- And further comprising at least one of titanium ion, citrate ion and ammonium ion as a main material of nickel or cobalt ions in order to improve surface quality so as to perform nickel chloride strike correction plating;
3) Wet electricity with at least one element of Zn, Cr, Fe, In, Cd, Zr, Ti, Co, Ni, Sn, Pb, Bi, Cu, Pd, Ag, Pt, Au, Os, Performing plating;
≪ / RTI >
The wet electroplating method according to claim 1, wherein the citric acid ion is obtained by dissolving one of citric acid, sodium citrate, potassium citrate, and ammonium citrate in the nickel chloride strike correction plating process.
The wet electroplating method according to claim 1, wherein the ammonium ion in the nickel chloride strike correction plating process is obtained by dissolving any one of ammonium chloride, ammonium sulfate, and ammonium nitrate in water.
The wet electroplating method according to claim 1, wherein the titanium ions in the nickel chloride strike correction plating step are obtained by reacting any one of titanium sulfate, titanium tetrachloride and titanyl sulfate with citric acid ions.
In an electroplating process in which nickel sulfide plating is carried out.
1) plating the plated body with sulfamic acid nickel strike;
2) After the sulfamic acid nickel strike plating, the growth direction of the plated sulfamate nickel strike plating layer was changed to a non-oriented non-cultured fine flat plating layer according to the removal of the bad phenomenon of the nickel sulfide plated layer of sulfamates and the shape of the plated body, Performing nickel-strike correction plating further comprising at least one of titanium ions, citric acid ions, and ammonium ions with nickel or cobalt ions as a main material in order to improve the performance of the plating;
3) Wet electricity with at least one element of Zn, Cr, Fe, In, Cd, Zr, Ti, Co, Ni, Sn, Pb, Bi, Cu, Pd, Ag, Pt, Au, Os, And performing a plating process on the wet electroplating process.

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