JP5937320B2 - Method for removing impurities from plating solution - Google Patents

Description

  The present invention relates to a method for removing impurities from a tin plating solution.

  In recent years, electroless tin plating has been widely used as plating on mechanical parts, flexible substrates, printed wiring boards, circuit patterns of electronic parts, and the like. These electroless tin platings are often performed as displacement tin platings on copper or copper alloys. When substitution tin plating is continuously performed on the copper or copper alloy plating, the substituted copper becomes copper ions and dissolves in the plating bath, and the copper ions accumulate as the plating progresses. Since the accumulated copper ions deteriorate the plating film and reduce the performance of the bath, the bath needs to be renewed.

  As a plating solution management method, a batch method and a feed-and-bleed method are known. The batch method is a method in which a new plating bath is rebuilt when the plating bath deteriorates. In an electroless tin plating bath, the plating bath is renewed each time the copper concentration increases and the performance of the bath decreases. There are problems such as an increase in the number of bathing man-hours, a decrease in productivity, and an increase in the cost of disposal of the waste bath. In addition, the feed and bleed method is a method in which plating is continuously performed while overflowing the plating solution, and copper can be removed from the system by overflow without stopping the plating operation, but a large amount of plating solution is replenished. Was necessary, which was also a factor in increasing costs.

  Various methods have been proposed as methods for solving these problems. For example, Patent Document 1 describes a method in which a part of a bath solution is taken out and cooled to precipitate a copper thiourea complex in the bath, the copper thiourea complex is removed by filtration, and the filtrate is returned to the original plating tank. ing. Patent Document 2 describes a method in which a copper thiourea complex is precipitated by cooling the bath liquid to 40 ° C. or lower by performing substantially the same operation as in Patent Document 1, and then filtering and removing the copper thiourea complex.

  In Patent Document 3, a regeneration cell having an anode, a cathode, and a cation / anion exchange membrane is used. In the electrolytic cell, copper is electrolytically deposited on the anode, and tin ions that permeate the cation exchange membrane are deposited. In addition to the plating solution after electrolysis, a method of returning to the plating tank is described. Furthermore, Patent Document 4 describes a method for oxidizing and decomposing a copper thiourea complex.

  However, according to the research of the present inventors, the treatment by the methods described in Patent Document 1 and Patent Document 2 is insufficient in removing copper, and therefore, a method capable of removing copper to a lower concentration is required. Become. The method described in Patent Document 3 requires an electrolytic cell for regeneration, and the apparatus becomes complicated. Further, the method described in Patent Document 4 requires a drug and a device for oxidatively decomposing a copper thiourea complex.

JP-A-5-222540 JP 2002-317275 A JP-A-10-317154 JP-A-4-276082

  An object of the present invention is to provide a method capable of removing impurities in a tin plating solution to a lower concentration than a conventional method without requiring a special apparatus for removing impurities in the tin plating solution. That is.

  As a result of diligent studies to solve the above-mentioned problems, the present inventor has obtained an additive containing an aromatic organic sulfonic acid or a salt thereof in an electroless tin plating solution containing a nonionic surfactant and a thiourea or thiourea compound. It was found that the impurity concentration in the plating solution can be further reduced as compared with the conventional method by adding a precipitate to form a precipitate under cooling, and the present invention has been completed.

  According to the first method of the present invention, an additive containing an aromatic organic sulfonic acid or a salt thereof is added to a tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound. In this method, impurities are removed from the plating solution by generating precipitates.

  In the second method of the present invention, after electroless tin plating is performed on copper or a copper alloy using an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound, the electroless This is a method for regenerating a plating solution in which an additive containing an aromatic organic sulfonic acid or a salt thereof is added to a tin plating solution, and precipitates generated under cooling are removed.

  A third method of the present invention is a method of forming an electroless tin plating film using an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound, the electroless tin plating film A part or all of the plating solution is circulated from the plating tank for tin plating to the plating tank via a solid-liquid separator, and an additive containing aromatic organic sulfonic acid or a salt thereof is added to the plating liquid. A method for forming a plating film, in which deposits generated by cooling the plating solution are captured and removed by the solid-liquid separator.

The fourth method of the present invention includes a main tank for performing electroless tin plating, a precipitation tank for forming precipitates, and a circulation for connecting an electroless tin plating solution between the main tank and the precipitation tank so that the electroless tin plating solution can be circulated. Using a multi-tank type plating apparatus having a solid-liquid separator installed between the pipe and the precipitation tank to the main tank, using a tin plating solution containing a nonionic surfactant and thiourea or thiourea compound A method of performing electroless plating on an object to be plated,
(A) adding an additive containing an aromatic organic sulfonic acid or a salt thereof to the plating solution in the precipitation tank;
(B) a step of cooling the plating solution, and (C) a step of capturing precipitates generated under cooling using a solid-liquid separator, the order of (A), (B), (C), Or it is the plating method which performs each process in order of (B), (A), (C).

  The fifth method of the present invention includes a plating tank for storing a plating solution and performing electroless tin plating, a circulation pipe connected to the plating tank so that part or all of the plating solution can be circulated, and a circulation path for the plating solution Uses a single tank type plating device with a solid-liquid separator installed in the tank and a temperature control device that cools or heats the plating solution in the plating tank, and contains a nonionic surfactant and a thiourea or thiourea compound A method of performing electroless tin plating on an object to be plated using a tin plating solution that comprises immersing the object to be plated in a plating solution in a plating tank, and adding an aromatic organic sulfonic acid or a salt thereof to the plating solution. It is a plating method which has the process of adding the additive which contains and producing | generating a precipitate under cooling, and removing the produced | generated precipitate from a plating solution using the said solid-liquid separator.

  A sixth method of the present invention is a method for managing an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound for performing electroless tin plating on copper or a copper alloy. A method for managing a plating solution in which an additive containing an aromatic organic sulfonic acid or a salt thereof is added to the plating solution to produce a precipitate under cooling, thereby reducing the copper ion concentration in the plating solution.

  The method of the present invention does not require a special apparatus for performing oxidative decomposition or the like, and can reduce impurities in the plating solution to a lower concentration than the conventional method. Moreover, by removing impurities, the plating solution can be used over a long period of time, and the number of times of discarding the plating solution and performing a new bath can be drastically reduced. Therefore, it can greatly contribute to the improvement of industrial productivity.

  In this specification and claims, ° C. indicates degrees Celsius, g indicates grams, L indicates liters, mL indicates milliliters, dm indicates decimeters, and μm indicates microns or micrometers. . All amounts are percent by weight unless otherwise stated. In the present specification and claims, “plating solution” and “plating bath” have the same meaning and are used interchangeably. In the present specification and claims, the term “tin plating solution” means not only “tin plating solution” but also “tin alloy plating solution”. Similarly, the term “electroless tin plating solution” means not only “electroless tin plating solution” but also “electroless tin alloy plating solution”.

  In the present invention, the target plating solution is a tin plating solution, and an electroless tin plating solution is particularly preferable. Further, substitution tin plating (or substitution tin alloy plating) can be performed on copper or a copper alloy. A tin plating solution is preferred. Here, as described above, the terms “tin plating solution” and “electroless tin plating solution” include those containing metal components other than tin. The tin plating solution may contain a water-soluble tin salt or a water-soluble tin salt and other metal salts, a nonionic surfactant, and thiourea or a thiourea compound as a complexing agent.

  The water-soluble tin salt used in the tin plating solution may be any as long as it dissolves in water when the plating solution is used. For example, stannous sulfate, stannous chloride, tin borofluoride, alkane Tin sulfonate, tin alkanol sulfonate and the like can be used.

  Other metal salts that can be used with the water-soluble tin salt include salts of lead, copper, silver, bismuth, cobalt, etc. Specifically, lead chloride, lead acetate, lead alkanesulfonate , Copper chloride, silver nitrate, bismuth chloride, cobalt sulfate and the like.

  The total content of tin and metal components other than tin in the plating solution is usually 10 to 100 g / L, preferably 30 to 50 g / L as a metal.

  An acid may be added to the tin plating solution for the purpose of dissolving tin or metal components other than tin. Examples of the acid to be used include sulfuric acid, hydrochloric acid, alkane sulfonic acid, alkanol sulfonic acid, aromatic sulfonic acid and the like, and these acids can be used singly or in combination. The amount of acid added to the plating solution is generally 1 to 300 g / L, preferably 50 to 100 g / L in total.

  The tin plating solution used in the present invention contains thiourea or a thiourea compound. These can act as complexing agents for eluting metals such as copper. Thiourea or thiourea compounds are well known to those skilled in the art as components to enable displacement tin plating on copper or copper alloys, which is theoretically impossible from a standard electrode potential relationship from an electrochemical standpoint. It has been. As thiourea, those which are usually available can be used, and commercially available ones can also be used.

  The thiourea compound is a derivative of thiourea such as 1-methylthiourea, 1,3-dimethyl-2-thiourea, trimethylthiourea, diethylthiourea, N, N-diisopropylthiourea, 1- (3- Hydroxypropyl) -2-thiourea, 1-methyl-3- (3-hydroxypropyl) -2-thiourea, 1-methyl-3- (3-methoxypropyl) -2-thiourea, 1,3-bis ( 3-hydroxypropyl) -2-thiourea, allylthiourea, 1-acetyl-2-thiourea, 1-phenyl-3- (2-thiazolyl) thiourea, benzylisothiourea hydrochloride, 1-allyl-2-thio Examples include urea and 1-benzoyl-2-thiourea. These thiourea or thiourea compounds can be used singly or in combination. The amount of these thiourea or thiourea compounds used is usually 50 to 250 g / L, preferably 100 to 200 g / L.

  The tin plating solution used in the present invention contains a nonionic surfactant. Nonionic surfactants include octylphenol type nonionic surfactants, alkylamine type nonionic surfactants, alkyl ether type nonionic surfactants, block polymer type nonionic surfactants, and naphthyl ether type nonionic surfactants. Activators can be used, and specifically, polyoxyethylene octylphenol, polyoxyether β naphthyl ether, polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene cetyl ether, etc. Can do. Of these, polyoxyethylene alkyl ether, polyoxyethylene octylphenol, and polyoxyethylene alkylamine are particularly preferable.

These nonionic surfactants can be used singly or in combination. The usage-amount of these nonionic surfactants is 1-100 g / L normally, Preferably it is 5-50 g / L.

  In addition to the above components, the tin plating solution may contain an antioxidant or the like as necessary. As the antioxidant, catechol, hydroquinone, hypophosphorous acid and the like can be used.

  In displacement plating (electroless tin plating), a plating solution is usually applied and the temperature is adjusted to 50 to 75 ° C., and then a plating object having a metal such as copper or copper alloy on the surface is plated for 120 to 300 seconds. It is performed by dipping in. Tin is replaced with a metal on the object to be plated such as copper on the surface of the object to be plated to form a tin film. Instead, the metal on the object to be plated such as copper is dissolved in the plating solution. For this reason, tin in the plating solution is consumed with the progress of plating. In addition, thiourea or thiourea compounds, which are complexing agents, are thought to form complexes with metals on the plating object such as copper in the plating solution, and these thiourea or thiourea compounds also decrease as the plating progresses. To do. Further, the acid and other components decrease (pump out) as the object to be plated is pulled up, and also decrease as the plating progresses. These components that decrease from the plating solution as the plating progresses are appropriately supplemented. However, elution metals such as copper increase with the progress of plating and accumulate in the bath, so that the plating film deteriorates and the performance of the bath deteriorates.

  In the present invention, an additive containing an aromatic organic sulfonic acid or a salt thereof (hereinafter also referred to as “aromatic organic sulfonic acids”) in a tin plating solution containing a nonionic surfactant, particularly an electroless tin plating solution. And a precipitate containing an elution metal such as copper which is an impurity is generated under cooling, and accumulation of the elution metal such as copper in the plating solution is suppressed. When an additive containing an aromatic organic sulfonic acid is added to the plating solution and the plating solution is cooled, an elution metal complex such as a copper ion complex dissolved in the plating solution is precipitated. The concentration of eluted metal ions such as copper ions can be reduced. “Precipitating the precipitate under cooling” means cooling the plating solution within the range in which precipitation does not precipitate when the precipitate is precipitated by adding an additive containing aromatic sulfonic acids to the plating solution. This includes both cases where an aromatic sulfonic acid additive is added later to precipitate a precipitate.

  The concentration of elution metal such as copper in the plating solution after the precipitation is generated by the method of the present invention is much lower than that of the prior art method. Although the detailed reaction mechanism is unknown, it is considered that elution metal ions such as copper ions exist in the plating solution as thiourea or thiourea compound complexes. Nonionic surfactants and aromatic organic sulfonic acids If present, the solubility of the thiourea or thiourea compound complex at low temperatures is decreased, thereby forming a precipitate. Nonionic surfactants are considered to be involved in the formation of precipitates together with aromatic organic sulfonic acids, and a specific nonionic surfactant should be selected for more efficient precipitation formation. Can do.

  As described above, the additive added to the tin plating solution in the present invention includes aromatic organic sulfonic acid or a salt thereof. Herein, the term “aromatic organic sulfonic acid” in the present specification and claims means an aromatic organic sulfonic acid and / or a hydrate thereof. The term “including an aromatic organic sulfonic acid or a salt thereof” includes not only the case of containing either one of an aromatic organic sulfonic acid and a salt of an aromatic organic sulfonic acid, but also the case of containing both of them. . Examples of the aromatic organic sulfonic acid include phenol sulfonic acid, benzene sulfonic acid, toluene sulfonic acid and naphthalene sulfonic acid, and hydrates of the above aromatic organic sulfonic acid. The salt of aromatic organic sulfonic acid may be any salt, and examples thereof include sodium salt, potassium salt, ammonium salt and the like. Aromatic organic sulfonic acids and their salts may be used as a mixture.

  The additive containing an aromatic organic sulfonic acid or a salt thereof may contain other components other than the aromatic organic sulfonic acids. For example, components that are consumed or reduced as the plating progresses (eg, nonionic surfactants, thioureas, thiourea compounds, and acids) can be included in the additive, and by the addition of such additives These components can be supplemented to the plating solution. The additive may be either solid or liquid. For example, the additive may be in the form of an aqueous solution in which aromatic organic sulfonic acids and any other components are dissolved in water. By making the additive into the form of an aqueous solution, it becomes easy to control the addition amount of the aromatic organic sulfonic acids and any other components.

The amount of additive added is usually such that the concentration of the aromatic organic sulfonic acid or salt thereof in the tin plating solution is 5 to 200 g / L, preferably 20 to 100 g / L, more preferably 50 to 100 g. / L is the amount. If the amount used is small, no precipitate is formed. In order to obtain sufficient precipitation, it is preferable to use it in such an amount that the concentration of the aromatic organic sulfonic acid or a salt thereof is 20 g / L or more. If the amount used is too large, deterioration of the bath performance such as deterioration of the precipitation state of tin and reduction of the precipitation rate occurs.
The amount of the additive added is desirably determined by the copper concentration in the bath. In order to remove 1 g of copper, 1-30 g of aromatic organic sulfonic acid or a salt thereof, preferably 1-20 g, more preferably 2-10 g. If the amount added is small, no precipitate is formed. When an excessive amount is added and a large amount of aromatic organic sulfonic acid remains in the bath after removing copper, bath performance such as deterioration of the precipitation state of tin and reduction of the precipitation rate occurs.

According to the first method of the present invention, an additive containing an aromatic organic sulfonic acid or a salt thereof is added to a tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound. In this method, impurities are removed from the plating solution by generating precipitates.
Here, it is preferable that the tin plating solution to which the additive containing aromatic organic sulfonic acids is added is already used for tin plating, particularly electroless tin plating. In the case of electroless tin plating, if the solution is already used for electroless tin plating, it is the plating solution after the electroless tin plating process is completely completed, or the electroless tin plating process is in the middle It doesn't matter. Impurities include copper and other metal species (for example, nickel, zinc, chromium, molybdenum, tungsten, etc.) eluted from the object to be plated. The impurity is particularly copper, and the present invention can effectively remove copper from the plating solution. As described above, when an additive containing an aromatic organic sulfonic acid is added to a plating solution used for plating in which the concentration of eluted metal such as copper is increased, an insoluble component containing eluted metal such as copper is deposited under cooling. . By removing this insoluble component, the eluted metal such as copper can be removed from the plating solution. Arbitrary methods can be used for the removal of the insoluble matter, and for example, methods such as filtration using a filter, precipitation separation, and centrifugation can be used.

In the second method of the present invention, after electroless tin plating is performed on copper or a copper alloy using an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound, the electroless This is a method for regenerating a plating solution in which an additive containing an aromatic organic sulfonic acid or a salt thereof is added to a tin plating solution, and precipitates generated under cooling are removed.
As described above, impurities, particularly eluting metals such as copper, can be removed from the plating solution by adding an additive containing aromatic organic sulfonic acids to the plating solution and removing the precipitate deposited under cooling. it can. The plating solution after removing the deposit can be reused, and can be continuously used as a plating solution by supplementing other components that have been consumed or reduced. For this reason, it is not necessary to discard the aged plating solution, and industrial productivity can be improved. Replenishment of other components consumed or reduced may include supplemental components (eg, nonionic surfactants, thioureas, thiourea compounds, tin and acids, etc.) in the additive along with aromatic organic sulfonic acids. It can be done by adding.

A third method of the present invention is a method of forming an electroless tin plating film using an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound, the electroless tin plating film A part or all of the plating solution is circulated from the plating tank for tin plating to the plating tank via a solid-liquid separator, and an additive containing aromatic organic sulfonic acid or a salt thereof is added to the plating liquid. In this method, a deposit formed by cooling is captured and removed by the solid-liquid separator.
Also in this method, the plating solution may be cooled before the addition of the additive containing the aromatic organic sulfonic acids within the temperature range in which precipitates do not appear, and the aromatic organic sulfonic acids are contained. You may cool to the temperature which a precipitate produces | generates after adding an additive. It is preferable to circulate the electroless tin plating solution after temporarily suspending the plating operation. Addition of additives including aromatic organic sulfonic acids is also performed by temporarily suspending the plating operation to replenish the necessary components of the plating solution consumed or reduced in the plating solution after removing the precipitate and plating the plating solution. It is preferable to heat up to a temperature suitable for the above and then resume the plating. The replenishment of the necessary components can be performed by adding the necessary components (for example, nonionic surfactant, thiourea, thiourea compound, and acid) together with the aromatic organic sulfonic acids.

  Any solid-liquid separation apparatus can be used as long as it can separate the plating solution and the generated precipitate, and apparatuses such as filtration using a filter, precipitation separation, and centrifugation can be used. Here, the addition of the additive containing aromatic organic sulfonic acids is applied to the plating solution deteriorated by the plating operation, that is, in the process of plating the object to be plated, from the object to be plated, copper, nickel, zinc, It is preferable to carry out with respect to a plating solution in which metal ions such as chromium, molybdenum and tungsten are eluted and the bath performance is lowered. As described above, the plating film is formed with a tin plating solution, for example, after the temperature of the plating solution is adjusted to 50 to 75 ° C., and then an object to be plated having copper or a copper alloy on its surface is 120 to 300. It is performed by dipping in the plating solution for 2 seconds. Copper ions elute into the plating solution as the plating progresses, so the addition of additives containing aromatic organic sulfonic acids, cooling of the plating solution, circulation, and the trapping and removal of deposits are performed in the required timing and order. Can be done.

The fourth method of the present invention includes a main tank for performing electroless tin plating, a precipitation tank for forming precipitates, and a circulation for connecting an electroless tin plating solution between the main tank and the precipitation tank so that the electroless tin plating solution can be circulated. Using a multi-tank type plating apparatus having a solid-liquid separator installed between the pipe and the precipitation tank to the main tank, using a tin plating solution containing a nonionic surfactant and thiourea or thiourea compound A method of performing electroless plating on an object to be plated,
(A) adding an additive containing an aromatic organic sulfonic acid or a salt thereof to the plating solution in the precipitation tank;
(B) a step of cooling the plating solution, and (C) a step of capturing precipitates generated under cooling using a solid-liquid separator, the order of (A), (B), (C), Or it is the plating method which performs each process in order of (B), (A), (C).
The fourth method of the present invention is characterized by using a multi-tank type apparatus provided with a deposition tank for forming a precipitate in addition to a main tank for performing electroless plating. Although at least two tanks are required, it is good also as three or more tanks as needed. The main tank and the precipitation tank can be of any size and shape as long as plating treatment and precipitate generation can be performed. Temperature control equipment is preferably installed in the main tank and the precipitation tank, and heating is mainly performed in the main tank and cooling is mainly performed in the precipitation tank. The main tank and the precipitation tank are connected by piping so that the electroless plating solution can be circulated between the two tanks. The piping can be in any form as long as the plating solution can be circulated. Moreover, a solid-liquid separator is installed in the middle of the flow of the plating solution from the precipitation tank to the main tank, and precipitates generated under cooling can be separated by addition of an additive containing aromatic organic sulfonic acids. As described above, any solid-liquid separator can be used. Steps (A) to (C) may be performed in the order of (A), (B), and (C), or may be performed in the steps of (B), (A), and (C).

  Regardless of the order, the deposit can be generated in the precipitation tank while the plating operation is continued in the main tank, and it is advantageous in that it is not necessary to pause the plating operation. The temperature of the plating solution in the main tank is preferably 50 to 75 ° C, and the temperature of the plating solution in the precipitation tank is preferably in the range of 5 to 30 ° C. Addition of an additive containing aromatic organic sulfonic acid or a salt thereof to the plating solution in the step (A), cooling of the plating solution in the step (B), and the precipitate produced in the step (C) as a solid liquid The method of capturing using the separation device is as described above.

The fifth method of the present invention includes a plating tank for storing a plating solution and performing electroless tin plating, a circulation pipe connected to the plating tank so that part or all of the plating solution can be circulated, and a circulation path for the plating solution Uses a single tank type plating device with a solid-liquid separator installed in the tank and a temperature control device that cools or heats the plating solution in the plating tank, and contains a nonionic surfactant and a thiourea or thiourea compound A method of performing electroless plating on an object to be plated using a tin plating solution, wherein (A) a step of immersing the object to be plated in a plating solution in a plating tank, (B) an aromatic organic sulfone in the plating solution A plating method comprising: a step of adding an additive containing an acid or a salt thereof to generate a precipitate under cooling; and (C) a step of removing the generated precipitate from the plating solution using the solid-liquid separator. .
The fifth method of the present invention is characterized in that a single tank type plating apparatus is used in order to generate a precipitate by adding an additive containing aromatic organic sulfonic acids to a plating tank for performing electroless plating. As the plating tank, one having a size and shape capable of plating treatment and generation of precipitates can be used. As long as the temperature management device can adjust the plating solution to a desired temperature, it can be used in any form. Arbitrary forms can be used for the circulation pipe and the solid-liquid separator as described above.

  In the step (A), the object to be plated is immersed in a plating solution in a plating tank to perform displacement plating. The temperature of the plating solution in the plating tank is preferably 50 to 75 ° C. As displacement plating proceeds in the plating tank, copper ions dissolved from the object to be plated accumulate in the plating solution. In the step (B), an additive containing aromatic organic sulfonic acids is added to the plating solution in the plating tank. The addition method is as described above. Moreover, in the process of (B), the plating solution in the plating tank which added the additive containing aromatic organic sulfonic acids is cooled. The cooling may be performed before or after the additive containing the aromatic organic sulfonic acid is added. As described above, the temperature of the plating solution during cooling is preferably 5 to 30 ° C. When performing the process of (B), since plating temperature becomes lower than the range suitable for plating, it is necessary to stop plating operation. In the step (C), the precipitate generated in the plating tank is sent to a solid-liquid separator via a circulation pipe and separated and removed from the plating solution. It is necessary to circulate the plating solution after the step (B) is completed.

A sixth method of the present invention is a method for managing an electroless tin plating solution containing a nonionic surfactant and thiourea or a thiourea compound for performing electroless tin plating on copper or a copper alloy. A method for managing a plating solution in which an additive containing an aromatic organic sulfonic acid or a salt thereof is added to the plating solution to produce a precipitate under cooling, thereby reducing the copper ion concentration in the plating solution.
In the plating tanks of the various forms described above, the copper concentration in the plating solution is measured, and additives containing aromatic organic sulfonic acids are added to the plating solution at an appropriate time before the copper concentration reaches the upper limit that adversely affects plating. Subsequently, the plating solution to which an additive containing aromatic organic sulfonic acids is added is cooled to generate precipitates, thereby reducing the copper ion concentration in the plating solution and bringing the electroless plating solution to an optimum state. Can be managed. The copper ion in the plating solution can be measured by any method. For example, a part of the plating solution can be extracted and the copper ion concentration can be measured by atomic absorption or ICP.

Reference Examples 1 and 2 and Examples 3 -5
An electroless tin plating solution having the following composition was prepared.
・ Tin borofluoride (as Sn ²⁺ ) 37g / L
・ Methanesulfonic acid 50g / L
・ Hypophosphorous acid 30g / L
・ Thiourea 100g / L
-Nonionic surfactant of Table 1 50 g / L

  Add 20 g / L of copper powder to each of the above tin plating solutions, heat at 65 ° C. for 5 hours with stirring, complete the substitution reaction of copper and tin, and add a deteriorated electroless tin plating solution containing copper ions. Simulated. While maintaining the above simulated deteriorated plating solution at 65 ° C., 70 g / L of paratoluenesulfonic acid was added as an additive, and then the plating solution was cooled to 25 ° C. After cooling the plating solution, floating substances were generated in the plating solution. The floating substance was removed through a filter (0.2 micron), and the copper concentration in the plating solution after filtration was measured by atomic absorption. The results are shown in Table 2.

Example 6
Benzenesulfonic acid was used instead of the paratoluenesulfonic acid of Example 4, and benzenesulfonic acid was added as an additive to the simulated deterioration plating solution containing copper ions maintained at 65 ° C. as in Example 4, followed by The plating solution was cooled to 25 ° C. After cooling the plating solution, floating substances were generated in the plating solution. The generated floating substance was allowed to settle, the supernatant liquid was sampled, and the copper concentration in the sampling liquid was measured by atomic absorption. The measured copper concentration was 0.4 g / L.

Example 7
A deteriorated electroless tin plating solution containing copper ions was produced in a simulated manner by the same operation as in Example 3. The simulated deterioration plating solution was cooled to 30 ° C. At this time, no floating substances were generated. While maintaining the simulated deterioration plating solution at 30 ° C., 70 g / L of paratoluenesulfonic acid was added. Immediately after the addition, floating substances were generated in the plating solution. The floating substance was removed through a filter (0.2 micron), and the copper concentration in the plating solution after filtration was measured by atomic absorption. The measured copper concentration was 0.9 g / L.

Comparative Example 1
The same operation as in Reference Example 1 was carried out except that a nonionic surfactant was not used, and the copper concentration in the plating solution after filtration was measured by atomic absorption. The results are shown in Table 3.
Without the non-ionic surfactant, the copper removal rate is seen that bad in comparison with Reference Examples 1 and 2 and Examples 3 -7, also aromatic organic sulfonic acids are not consumed.

Comparative Example 2
The same operation as in Reference Example 2 was performed except that isethionic acid was used instead of paratoluenesulfonic acid, and the copper concentration in the plating solution after filtration was measured by atomic absorption. The measured copper concentration was 7.2 g / L.

Comparative Example 3
The same operation as in Reference Example 2 was performed except that isethionic acid was used instead of paratoluenesulfonic acid and a nonionic surfactant was not used, and the copper concentration in the plating solution after filtration was measured by atomic absorption. The measured copper concentration was 7.4 g / L.

Example 8
A repeated impurity removal test and a plating performance evaluation test after impurity removal were performed. Using the same plating solution as in Example 4, electroless tin plating was performed under the following conditions. Copper was added in the same manner as in Example 4 to prepare a simulated deteriorated plating solution, and electroless tin plating was similarly performed using this simulated deteriorated plating solution. Thereafter, paratoluenesulfonic acid was added in the same manner as in Example 4, and after cooling, impurities were filtered. Add the spent thiourea, nonionic surfactant (polyoxyethylene β-naphthyl ether), tin borofluoride, etc. to the plating solution after filtration, and adjust to the same concentration as the plating solution before adding copper. Electrolytic tin plating was performed. These operations were performed 4 times in total. The results are shown in Table 4.

Plating conditions: temperature 65 ° C; plating time 195 seconds

Claims (6)

Contains a nonionic surfactant selected from the group consisting of alkyl ether type nonionic surfactants, naphthyl ether type nonionic surfactants and block polymer type nonionic surfactants , and thiourea or thiourea compounds After performing electroless tin plating on copper or a copper alloy using an electroless tin plating solution, an additive containing an aromatic organic sulfonic acid or a salt thereof is added to the electroless tin plating solution, and under cooling A method of removing impurities from the electroless tin plating solution by generating precipitates. Contains a nonionic surfactant selected from the group consisting of alkyl ether type nonionic surfactants, naphthyl ether type nonionic surfactants and the like and block polymer type nonionic surfactants , and thiourea or thiourea compounds After electroless tin plating is applied to copper or copper alloy using electroless tin plating solution, an additive containing aromatic organic sulfonic acid or its salt is added to the electroless tin plating solution and produced under cooling A method for regenerating an electroless tin plating solution that removes deposits. Contains a nonionic surfactant selected from the group consisting of alkyl ether type nonionic surfactants, naphthyl ether type nonionic surfactants and the like and block polymer type nonionic surfactants , and thiourea or thiourea compounds A method of forming an electroless tin plating film on copper or a copper alloy using an electroless tin plating solution, wherein a solid-liquid separation device removes a part or all of the plating solution from a plating tank for performing the electroless tin plating. Circulate to the plating tank via, and add an additive containing an aromatic organic sulfonic acid or a salt thereof to the plating solution subjected to electroless tin plating, and the solid-liquid separation of precipitates generated under cooling A method of forming a plating film that is captured and removed by an apparatus. A main tank for performing electroless tin plating, a precipitation tank for forming precipitates, a circulation pipe for connecting an electroless tin plating solution between the main tank and the precipitation tank, and a deposition tank to the main tank A group consisting of alkyl ether type nonionic surfactant, naphthyl ether type nonionic surfactant, etc. and block polymer type nonionic surfactant , using a multi-tank type plating apparatus having a solid-liquid separation device installed between A method of performing electroless tin plating on an object to be plated having copper or a copper alloy on its surface using a tin plating solution containing a nonionic surfactant selected from thiourea or a thiourea compound,
(A) adding an additive containing an aromatic organic sulfonic acid or a salt thereof to the electroless tin plating solution subjected to electroless tin plating in the precipitation tank;
(B) a step of cooling the electroless tin plating solution, and (C) a step of capturing precipitates generated under cooling using a solid-liquid separator, (A), (B), (C) Or an electroless tin plating method in which each step is performed in the order of (B), (A), and (C). A plating tank for storing the plating solution and performing electroless tin plating, a circulation pipe connected to the plating tank so that part or all of the plating solution can be circulated, a solid-liquid separator installed in the circulation path of the plating solution, And a single tank type plating apparatus having a temperature control device for cooling or heating the plating solution in the plating tank, alkyl ether type nonionic surfactant, naphthyl ether type nonionic surfactant, etc. and block polymer type nonionic type Electroless tin plating on an object to be plated having copper or a copper alloy on its surface using a nonionic surfactant selected from the group consisting of surfactants and an electroless tin plating solution containing thiourea or a thiourea compound A step of immersing an object to be plated in a plating solution in a plating tank, and an aromatic organic sulfone in the plating solution subjected to electroless tin plating. Acid or steps, the precipitate formed has a step of removing from the plating solution by using the solid-liquid separator, an electroless tin plating method of forming a deposit under the addition of additives cooling salts thereof. Non-ion selected from the group consisting of alkyl ether type nonionic surfactants, naphthyl ether type nonionic surfactants and block polymer type nonionic surfactants for electroless tin plating on copper or copper alloys A method for managing an electroless tin plating solution containing a surfactant and thiourea or a thiourea compound, wherein after electroless plating is applied to copper or a copper alloy using the electroless tin plating solution, An electroless tin plating solution management method for reducing the copper ion concentration in a plating solution by adding an additive containing an aromatic organic sulfonic acid or a salt thereof to the electrolytic tin plating solution and generating precipitates under cooling .