JPH0364482A - Plating solution concentration measurement method, concentration adjustment method, and concentration adjustment device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a plating solution concentration measuring method, a concentration adjustment method, and a concentration adjustment device.

[Prior art] Generally, gold plating is used in the manufacture of wiring boards because it has excellent solderability, connectivity such as wire bonding, etching resistance, rust prevention, and electrical conductivity. It is considered an extremely important technology.

The gold plating solution used in electroless plating is usually a cyan-based plating solution because of its excellent stability. However, cyan-based plating solutions have problems in terms of pollution control, so in recent years, plating solutions have been developed that contain gold ions as metal components, thiosulfate ions and sulfite ions as ligands that form complexes with gold ions, and thiourea as a reducing agent. A non-cyanide electroless gold plating solution has been proposed.

Regarding changes in component concentration over time and plating speed when plating is performed using a non-cyanide plating solution,
This will be explained using FIGS. 6 and 7.

FIG. 6 shows changes in component concentrations when plating is proceeded without adding the components constituting the plating solution as a replenisher. Figure 7 shows changes in component concentration and plating speed when the concentration of the plating solution components is kept constant by adding components as a replenisher that decrease with the progress of plating.

In FIG. 6, the vertical axis represents the component a degree, and the horizontal axis represents the plating time.

As is clear from FIG. 6, as the plating progresses, the concentrations of sulfite ions and thiosulfate ions do not change, but the concentrations of gold ions and thiourea decrease. For this reason, the plating speed gradually decreases.

In FIG. 7, the vertical axis also shows the component a degree, and the horizontal axis shows the plating time. Furthermore, it also shows the change in plating speed with the passage of plating time.

As shown in Figure 7, by measuring the amount of gold and thiourea consumed as plating progresses at regular intervals and replenishing the amount consumed, the plating rate can be maintained within a certain range for a long time. be able to.

As described below, in electroless plating, both the metal component and the reducing agent component of the plating solution components are consumed as the plating progresses. Furthermore, since the electroless plating rate is highly dependent on the concentration of the plating solution components, in order to maintain a constant plating rate, the concentration of both the metal component and the reducing agent component must be measured and the amount consumed must be calculated sequentially. Needs to be replenished.

Here, to measure the concentration of each component, for example, use an atomic absorption spectrophotometer for metal components, use the sodium nitroprusside method for thiourea as a reducing agent, and use ion chroma 1-1 for sulfite ions and thiosulfate ions. This can be done using the law.

(The following is a blank space) [Problems to be solved by the invention] However, in the above-mentioned method for quantitative analysis of cyanide plating solution components, it is necessary to dilute the sample solution each time due to the high sensitivity of the atomic absorption method. , and also two I. to analyze thiourea.
Loplusi-1-1-lium is easily decomposed. For this reason,
Measurement takes time, and although it is used for laboratory-level analysis, it is not suitable for analysis of manufacturing processes.

Regarding the concentration measurement of metal components in the electroless plating solution, as proposed in JP-A-63-121668, there is a method of measuring by spectrophotometry using the coloring of the metal ions themselves; Alternatively, a method using fluorescent X-ray analysis as described in JP-A-60-164239, or a method using potentiometric titration as described in JP-A-62-14053, etc. be.

Regarding the concentration measurement of reducing agent components such as formalin in the electroless plating solution, there is a method of measuring from the amount of current required to oxidize the reducing agent, as described in JP-A-53-9235. .

However, among the two conventional techniques, the methods that utilize coloring of metal components and the method that utilizes potentiometric titration have the problem that the types of electroless plating solutions that can be applied are limited, and they lack versatility. .

On the other hand, with regard to the method for measuring the concentration of the reducing agent component, no consideration has been given to electroless plating solutions that contain large amounts of reducing ions such as sulfite ions and thiosulfate ions as complexing agents in addition to the reducing agent.

For example, when measuring the concentration of a reducing agent from the amount of current required to oxidize the reducing agent, sulfite ions are used.

Since thiosulfate ions are also oxidized at the same time, it is not possible to accurately measure the component concentration of the reducing agent.

As described above, conventional plating technology, particularly electroless plating technology, has had the problem that there is no technology that can accurately measure the component concentration of the plating solution during the manufacturing process, and therefore, the component concentration cannot be properly controlled. Ta.

A first object of the present invention is to provide a method for measuring the concentration of components in a plating solution, a method for controlling the concentration of components in the plating solution within a certain range, and an apparatus therefor.

A second object of the present invention is to provide a plating apparatus that can control the concentration of components in a plating solution within a certain range.

A third object of the present invention is to provide an apparatus that can measure the concentrations of metal I components and non-metal components contained in a solution and control the concentration of the solution within a certain range.

[Means for Solving the Problems] A first object of the present invention is to provide a method for measuring the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: After substituting other anion species that do not interfere with the measurement, 1 iL! This is achieved by a plating solution component concentration measurement method that is characterized by measuring the reducing agent concentration.

A method for measuring the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: replacing the anion with another anion species that does not interfere with the measurement of the concentration of the reducing agent; This is achieved by a method for measuring the component concentration of a plating solution, which is characterized in that the concentration of the metal component is measured by atomic absorption spectrometry or plasma emission spectrometry.

It is preferable that the reducing agent concentration is measured with an ultraviolet absorption detector or a potentiometric titration device.

A method for measuring the component concentration of a plating solution containing a metal component, a reducing ion, and a nonionic reducing agent, the method comprising replacing the reducing ions with nonionic ions, and then measuring the concentration of the nonionic reducing agent. This can also be achieved by a method for measuring the concentration of components in a plating solution, which comprises measuring the concentration of the metal component.

Measuring the metal component concentration in the plating solution and calibrating the metal component concentration measuring means used for this measurement; measuring the reducing agent concentration in the plating solution and calibrating the reducing agent concentration measuring means used for this measurement; The operation of replacing the anion with another anion species that does not interfere with the measurement of the concentration of the reducing agent is performed under sequence control according to a preset sequence program, and further, the H1ll constant value determined by the measurement and the above This can also be achieved by a method for measuring the component concentration of a plating solution, which is characterized in that the metal fraction concentration and reducing agent concentration in the plating solution are determined by calculation from the calibration values obtained by calibration.

A method for adjusting the concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: replacing the anion in the plating solution with another anion species that does not interfere with the measurement of the concentration of the reducing agent; Comparison 1E of the metal component concentration measuring means for measuring the component and comparison n' of the reducing agent concentration measuring means for measuring the reducing agent component: and measurement of the metal component concentration by the metal component concentration measuring means and the reducing agent 'a. The consumption amount of the metal component concentration and the reducing agent concentration is determined by calculation using the calibration value and the measured value obtained from the measurement of the reducing agent concentration by the measuring means, and further, the amount of reducing agent and This can also be achieved by a method for adjusting the concentration of a plating solution, which comprises replenishing the plating solution with a replenisher containing a metal component.

A device for adjusting the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, comprising an ion exchange means for replacing the anion with an anion species that does not interfere with measurement of the concentration of the reducing agent; a regenerating means for regenerating the ion exchange means using a seven-volume solution containing seeds; a reducing agent concentration measuring means for measuring the reducing agent concentration; a metal component concentration measuring means for measuring the metal component concentration; Sequence control means for controlling calibration of the reducing agent concentration measuring means and the metal component concentration measuring means, and measurement of plating solution components by the reducing agent concentration measuring means and the metal component concentration measuring means;
The plating solution further comprises a calculation control means for calculating the metal component concentration and the reducing agent concentration in the plating solution from the measured value obtained by the measurement and the calibration value obtained by the calibration. This can also be achieved using a component concentration measuring device.

An apparatus for adjusting the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, the device comprising an ion exchange means for replacing the anion with an anion species that does not interfere with measurement of the concentration of the reducing agent, and the anion species. a regenerating means for regenerating the ion exchange means using a solution containing 5 6 , a reducing agent concentration measuring means for measuring the reducing agent concentration, a metal component concentration measuring means for measuring the metal component concentration, Sequence control means for controlling the operations of the reducing agent concentration measuring means and the metal component concentration measuring means, and determining the reducing agent and metal components from the difference between the measured values of the reducing agent concentration and the metal component concentration and their respective set concentrations. plating comprising: a calculation means for calculating the consumption amount; and an arithmetic control means equipped with a supply means for supplying a replenisher containing a reducing agent and a metal component corresponding to the consumption amount to the plating tank. This can also be achieved by a liquid component concentration adjustment device.

A second object of the present invention is a plating apparatus that performs plating using a plating solution containing a metal component, an anion, and a reducing agent, the plating apparatus comprising a plating tank, a plating solution concentration measuring means, and a plating solution replenisher. the plating solution concentration measuring means includes an ion exchange means for replacing the anion with another anion species that does not interfere with the measurement of the reducing agent concentration; comprising a reducing agent concentration measuring means for measuring the concentration of the plating solution and a metal concentration measuring means for measuring the concentration of the metal component, the sequence control means controlling the operation of the plating solution concentration measuring means, and the arithmetic control means controlling the reduction Calculation means for calculating the consumption amount of the reducing agent and metal component from the difference between the measured values of the agent concentration and metal fraction concentration and the respective set concentrations, and a replenisher containing the reducing agent and metal component corresponding to the consumption amount. This is achieved by a plating apparatus characterized by comprising a supply means for supplying the plating solution from the plating solution replenishment section to the plating tank.

A third object of the present invention is to provide a solution comprising: a metal component concentration measuring means for measuring the concentration of a metal component contained in a solution; and a non-metal component concentration measuring means for measuring a non-metal component concentration; A control function for controlling the operations of the concentration measuring means and the non-metal component concentration measuring means, and determining the concentration of the metal component and the non-metal component from the difference between the measured values of the concentration of the metal component and the concentration of the non-metal component and their respective set concentrations. This is achieved by a concentration control device characterized by having a similar function of supplying a replenisher containing a metal component and a replenisher containing a non-metal component corresponding to the consumption amount of the component.

The metal component concentration measuring means is preferably atomic absorption spectrophotometry or plasma emission spectrophotometry.

The nonmetal concentration measuring means includes an anion exchanger, and
More preferably, it is characterized by having an ultraviolet absorption detector or a potentiometric titration device.

[Function] The anion exchange material in the anion exchanger is regenerated into a chloride ion type using a regenerating solution, such as a KCQ (potassium chloride) solution, and a certain amount of the pyrolytic plating solution sample is poured into it. In this case, sulfite ions, thiosulfate ions, and complex ions such as those coordinated with metal ions in the plating solution have a greater affinity for anion exchange materials than chlorine ions. It is captured by the substance, and an equivalent amount of chlorine ion flows out in return.

On the other hand, since reducing agents such as thiourea and formalin contained in the electroless plating solution are non-ionic (raw), they are not captured by the anion exchange material and are eluted from the anion exchanger as they are.

In this way, reducing ions contained in the plating solution can be removed.

If the reducing agent contained in the plating solution is a substance that exhibits ultraviolet absorption, such as thiourea, the concentration of thiourea can be measured with an ultraviolet absorption detector provided after the anion exchanger. Furthermore, when the reducing agent is a substance that does not exhibit ultraviolet absorption, such as formalin, the concentration can be calculated from the amount of current required to oxidize formalin.

Examples of anion exchange materials include anion exchange resin columns,
An anion exchange membrane or the like can be used.

In addition to the KCQ solution, other salts of chloride ions, such as NaCQ, can be used as regenerating solutions for anion exchange materials.

NH4CQ, a solution can also be used. In addition to chlorine ions, it is also possible to use a solution of anions that have a low affinity for anion exchange materials, such as NaHCO3920~ and KHCO, and regenerate them into T(CO2 type).

On the other hand, the concentration of gold components contained in the plating solution is measured by atomic absorption spectrometry.

By the above measurement method, it is possible to measure the concentration of metal ions and reducing agent, which decrease in concentration as plating progresses.

The arithmetic control means determines the consumption amount of the component for the progress of plating from the difference between the measured concentration of the plating solution and the control concentration of the plating solution set in advance, and calculates the replenishment amount.

Then, the component concentration of the plating solution is always managed within a certain range by sequentially replenishing the depleted amount from the replenisher tank according to the information on the amount of consumable components. As a result, the plating speed can be kept constant.

E Examples Examples of the present invention will be described below in more detail based on the drawings. Note that the present invention is not limited to this.

Example-1 FIG. 1 shows K AuCQ 4. TNa2S○3 + N
FIG. 2 is an explanatory diagram showing an example of an apparatus used to measure the thiourea concentration in an electroless plating solution containing a2S 20° and thiourea as the i component.

As shown in Fig. 1, the a degree d1 setting of this embodiment includes a water tank 1 for storing water (r-r2o) which is a carrier liquid, and a regeneration tank 1 for storing a 0,2N-K CQ solution which is a regenerating liquid. Liquid tank 2
, using a measuring device equipped with metering pumps 3, 4, hexagonal valve 5, sampling loop 6, sample injection [136, anion exchanger 7, anion exchange membrane tube 8, ultraviolet absorption detector 9 and recorder 37] It is done.

The anion exchanger 7 is a double tube equipped with an anion exchange membrane tube 8 inside. The anion exchange membrane tube 8 was heated to 0.0 mQ/min using the metering pump 4 at a flow rate of 2 mQ/min.
．． The regenerating liquid of 2N-K CQ is sent to the regenerating liquid tank 2 to the outer cylindrical part of the anion exchange membrane tube 8, and is constantly regenerated into chlorine ion type. The carrier liquid (H20) is sent from the water tank 1 to the ultraviolet absorption detector 9 from within the anion exchange membrane tube 8 at a flow rate of 2 to Q/1 min.

When the six-way valve 5 is in the connected state shown by the solid line in FIG. be done.

Next, when the six-way valve 5 is switched and connected to the state shown by the dotted line in the figure, the carrier liquid (H2O) flows through the sampling loop 6, and the plating solution sample collected in the sampling loop 6 undergoes anion exchange. From the membrane tube 8 it is transported to an ultraviolet absorption detector 9.

Sulfite ions, thiosulfate ions and [A
Gold complex ions such as u(S,03)2] are captured on the anion exchange membrane, and chlorine ions are eluted instead and sent to the ultraviolet absorption detector 9 by the carrier liquid. Since thiourea, which is a reducing agent, is a nonionic substance, it is transported to the ultraviolet absorption detector 9 without being captured within the anion exchange membrane tube 8.

The measurement wavelength of the ultraviolet absorption detector 9 is set to 240 nm. Using this ultraviolet absorption detector 9, the thiourea concentration in the plating solution can be measured based on the principle described below.

That is, as is clear from the absorption curve shown in Figure 2, the ultraviolet absorption of thiourea shows maximum absorption at 235 nm, whereas chlorine ions eluted by ion exchange such as sulfite ions and thiosulfate ions have a maximum absorption at 235 nm. Shows no absorption.

Further, as plating progresses, thiourea is oxidized to produce urea, but as shown in FIG. 2, this urea also does not exhibit ultraviolet absorption.

Therefore, the ultraviolet absorption detector 90 wavelength is 235 to 24.
When set to Onm, the absorbance of only thiourea in the plating solution can be measured.

In addition, to calculate the thiourea concentration in the plating solution, use a thiourea standard solution with a set concentration, measure the absorbance in the same manner as for the two-layer method, and calculate the absorbance using a proportional calculation based on the absorbance. I can do it.

Further, the anion exchanger 7 includes an anion exchange membrane tube 8
In addition to the method using this method, a structure may be used in which two flat anion exchange membranes are stacked, and the plating solution sample whose concentration is to be measured is flowed on the inside, and the KCQ solution as a regenerating solution is flowed on the outside.

Example-2 Figure 3 shows electroless plating solution'! The configuration of an example of a component concentration adjusting device applied to position A is shown.

In this example, using the above device, K A, , uCQ,
.

Mainly Na25Oa+ Na2S2O3, thiourea etc.
We are adjusting the component concentration of the electroless plating solution used as a precipitate.

As shown in FIG. 3, the component concentration adjusting device of this embodiment has the following features:
A water tank ■ in which water, which is a carrier liquid, is distilled.

Regeneration liquid tank 2 for storing 0,2N-KCQ solution as regeneration liquid, metering pumps 3, 4, six-way valve 5, sampling loop 6, anion exchanger 7, anion exchange membrane tube 8
and an ultraviolet absorption detector 9. It should be noted that these devices have almost the same configuration as the reducing agent a degree measuring device shown in FIG. 1 of the above series.

The component concentration adjusting device of this embodiment further includes an atomic absorption photometer 135 as a means for measuring the gold component concentration of the plating solution, and an arithmetic control unit 10 that follows.

The component concentration adjusting device of this embodiment is provided with a water tank top, a total replenisher tank 14, and a thiourea replenisher tank 15 as means for adjusting the concentration of the plating solution in the plating tank 13. In addition, a total standard solution tank J soil and thiourea standard solution 4 is used to store calibration solutions used to calibrate the ultraviolet absorption detector 9 and the atomic absorption spectrometer 35.
1! +12.

Each of the above tanks, ultraviolet absorption detector 9 and atomic absorption photometer 3
The piping system connecting 5 is a metering pump 3,4゜25~27.
33, a six-way valve 5 with a sampling loop 6, a six-way valve 28 with a sampling loop 29,
It includes electromagnetic valves 16 to 22, cocoon holes 1-23 and 24, and a dilution tank 30.

The dilution tank 30 is connected to a nitrogen cylinder 32 via a solenoid valve 31, and the measurement liquid sent to the dilution tank can be stirred in a nitrogen stream.

The suction side of the metering pump 25 is connected to the cocoon hole 1 via 23 to electromagnetic valves 16 to 19, and the discharge side is piped to a dilution tank 30 via a six-way valve 28.

Electromagnetic valves 20 to 22 are connected to the suction side of the metering pump 26 via the eyebrow holes 1 to 24, and the plating tank 1 on the discharge side
3 is connected to the total replenisher tank 11 and the thiourea replenisher tank 15.

The water tank 1 is connected to the suction side of the metering pump 27, and the discharge side is piped to send water to a dilution tank 30 via a six-way valve 28.

A dilution tank 30 is connected to the suction side of the metering pump 27, and the discharge side is piped to communicate with the anion exchanger 7 via the six-way valve 5.

The arithmetic and control unit 10 controls on/off of the metering pumps 3, 4, 25-27 and 33, and solenoid valves 16-22 and 3.
1, switching control of the six-way valve 5°28, collection of data signals from the ultraviolet absorption detector 9 and atomic absorption photometer 35, calculation of concentration, calculation of the amount of replenisher to be refilled, etc. .

Furthermore, the arithmetic and control unit]0 supplies the required amount of replenisher to the plating tank 13 from the total replenisher tank 14 and the thiourea replenisher tank 15, and adjusts the component concentration of the plating solution to the set range. .

Although not shown, the arithmetic and control unit includes, for example, a central processing unit (CPU), a memory for storing the CPU's operating program, arithmetic data, etc., an output device for visually displaying the arithmetic results, data, and control signals. It is configured with a T/○ that performs input/output processing such as, an interface, an input device that gives instructions and evaluations from the outside, etc.

Next, the operation of each part when adjusting the concentration of the plating solution components in the plating tank 13 will be explained.

First, in response to a command from the arithmetic and control unit 10, the solenoid valve 19
, and rotate the metering pump 25.

A portion of the plating solution from the plating tank 13 is collected into the sampler loop 29 of the hexagonal valve 28. Metering pump 27
is opened for a certain period of time to feed a certain amount of H2O (water) into the dilution tank 30, but during the process, the plating solution sample collected in the sampling loop 29 is also simultaneously transferred to the dilution tank 30 by switching the six-way valve 28. Send it in.

Thereafter, the electromagnetic valve 31 is opened, nitrogen gas is flowed into the dilution tank 30 for a short time to stir the solution, and the plating solution is diluted to a predetermined ratio in the dilution tank 30. A portion of the diluted plating solution sample is sent to an atomic absorption spectrophotometer 35 by an autosampler 34, and the total concentration in the plating solution is measured.

On the other hand, by opening the metering pump 33, a part of the diluted plating solution sample is collected into the sampling loop 6 of the hexagonal valve 5, and the following procedure is carried out in the same manner as in the reducing agent concentration measuring device shown in FIG. The method measures the concentration of thiourea in the plating solution.

Note that the switching of these six-way valves, the movement of the metering pump, etc. are automatically controlled using the arithmetic and control device 10.

Calibration of the atomic absorption photometer 35 and the ultraviolet absorption detector 9 is as follows:
The gold standard solution stored in the gold standard liquid enrichment tank 11 and the thiourea standard solution stored in the thiourea standard solution tank 12 are used to control (set) concentrations of gold and thiourea in the plating solution. The concentration is adjusted and carried out at least 101 times in the same manner as in the case of measuring the component concentration of the plating solution.

The supplementary iTE 4rf obtained using the standard solution is stored in the arithmetic and control unit 10, and by proportional division with it,
Calculate the gold and thiourea concentrations in the plating solution, and further calculate their replenishment amounts based on the deviation from the control concentration.

Then, using the metering pump 26, the plating tank 13 is replenished with each replenisher from the total replenisher tank 14 and the thiourea replenisher tank 5 by the calculated replenishment amount.

That is, the concentration of gold and thiourea, the concentration of the gold and thiourea replenisher, the liquid volume in the plating tank 13, measured by the method described in "-",
Gold based on the flow rate of the metering pump 26.

By calculating the replenishment time of thiourea and sequentially opening the solenoid valves 20 and 2 for a predetermined period of time, the required amount of replenisher can be replenished.

In addition, after full replenishment and thiourea replenishment, the solenoid valve 22
Open it and wash the piping system with water.

(The following is a blank space) Example-3 FIG. 4 shows an example of a concentration control device different from that shown in FIG. 3.

Similar to the embodiment shown in FIG. 3, this embodiment uses an atomic absorption spectrophotometer and an ultraviolet absorption detector as measurement devices, but this embodiment additionally includes a pH electrode and an atomic The calibration method of the spectrophotometer and the piping system are different.

Contains KAuCQ4 as a gold component and has reducing properties.
An example of controlling the concentration of an electroless plating solution containing 2S 203r Na2S Oa + thiourea will be described.

The concentration control device of this embodiment includes an atomic absorption spectrophotometer 102 that measures the concentration of gold components in the plating solution, and a device that exchanges reducing anions such as sulfite ions and thiosulfate ions with non-reducing ions. An anion exchanger 202 equipped with an ion exchange membrane tube 201, and an ultraviolet absorption detector 203 that measures the concentration of thiourea, which acts as a reducing agent in the plating solution.
, a pH electrode 303 and a pH meter 302, a sequencer 501 equipped with a control #4 function that calibrates each measuring device and measures the concentration of plating solution components, and a calculation function that calculates the consumption amount of the plating solution components. and an arithmetic control means 401- having a supply control function for controlling the supply of consumed components.

The arithmetic and control device 401 is configured in substantially the same manner as the arithmetic and control device 10 shown in the second embodiment.

The sequencer 50 has a memory that stores preset program control procedures as a program, and a CPU that controls the operations of solenoid valves, metering pumps, six-way valves, etc. according to the programs stored in this memory. Prepared and configured.

The sequencer 501 operates according to instructions from the calculation control means 401.

In addition, in FIG. 4, the solid line is the piping system, and the broken line is the signal transmission path. The transmission path of the sequencer 50,'l is not shown.

Furthermore, the concentration control device of this example has an atomic absorption luminance of 1 (
A metal component standard solution tank 610 and a reducing agent addition solution tank 618 are used as standard solutions for calibrating the ultraviolet absorption detector 202, a reducing agent standard solution tank 611 stores a standard 32- solution for calibrating the ultraviolet absorption detector 203, and a pH electrode 302. A pH buffer tank 612 that stores a standard solution to be calibrated, a metal component replenisher 11111614 that replenishes metal ions consumed by plating, a reducing agent replenisher #11615 that replenishes reducing agent consumed by plating, and ρI- It has a pH adjustment solution replenishment tank 616 for adjusting T.

A regeneration solution that supplies anions to be flowed into the anion exchanger 202 is stored in a regeneration liquid tank 6]-9.

Further, water used for cleaning the piping and diluting the sample solution is stored in a water tank 617.

Plating, tanks 61 to 6
The replenishment liquid to be refilled in the tank 614 includes a metal component replenishment liquid tank 614,
Reducing agent replenisher tank 615 and pH adjusting solution replenisher tank 616
The liquid stored in is used.

The plating tanks 61 to 65 shown in FIG. 4 may be incorporated into the apparatus of this embodiment, or may be connected from outside the apparatus by a piping system.

Further, the number of plating tanks is not limited to five.

Each of the measuring devices and each of the solution tanks are connected by a piping system, and each piping system is provided with a solenoid valve, a manifold, a word valve, a six-way valve, and a metering pump depending on the purpose.

Each of the plating tanks 61 to 65 has a solenoid valve 6 on one side thereof.
26 to 630 are connected. One end of the solenoid valve 625 is connected to the water tank 61-7. The other of the solenoid valves 625 to 630 is connected to the three-way valve 650 via the manifold 64
is connected to one side.

The metal component standard solution tank 610 and the reducing agent standard solution tank 61-
1, pH buffer tank 6] 2, and Na2S703, which will be described later.
The solution tank 613 has electromagnetic valves 621 to 621 on one side, respectively.
624 is connected. One side of the solenoid valve 620 is connected to the water tank 6
It is connected to 17. The other of the solenoid valves 620 to 624 is
It is connected to one side of a three-way valve 650 via a manifold 640.

The remaining - side of the three-way valve 650 is connected to the suction side of the metering pump 651 for sample collection, and the discharge side of the metering pump 65↓ for sample collection is connected to one side of the six-way valve 660 having the sample loop 66↓. Connected to one port.

A flow cell 301 in which a pH electrode 302 is inserted is connected to another port of the six-way valve 660. A pH electrode 302 is inserted into the flow cell 301, and the pH measured there is displayed on a pTI meter 303.

The metering pump 652 whose suction side is connected to the top 7 of the water tank 6 has its discharge side connected to the dilution tank 670 via a six-way valve 660.
is connected to. Nitrogen gas is fed into the dilution tank 670 from a nitrogen gas cylinder 680 via a solenoid valve 681 . The solenoid valve 671 is used when discarding the solution in the dilution tank 670.

The suction side of the metering pump 656 is connected to piping for collecting a diluted sample that passes from the dilution tank 670 through a six-way valve 664 having a sample loop 665 and a six-way valve 666 having a sample loop 667.

The suction side of the metering pump 654 is connected to the reducing agent addition liquid tank 618 via a six-way valve 662 having a sample loop 663 . The suction side of metering pump 5 655 is connected to water tank 617, and the discharge side of metering pump 655 is connected to dilution tank 672 via six-way valves 662 and 664.

From the dilution tank 672, the sample to be measured is sent to the atomic absorption photometer 102 by the O1-sampler 101. Nitrogen gas is sent into the dilution tank 672 via a solenoid valve 682. The solenoid valve 673 is a solenoid valve for solution disposal.

The suction side of the metering pump 657 is connected to water W1617. Then, from the discharge side of the metering pump 657, the carrier liquid (H2O) is sent at a constant rate from the ion exchange membrane tube 201 to the ultraviolet absorption detector 203 via the six-way valve 666. The metering pump 658 is connected to the regenerating liquid tank 6
From there, the regeneration solution is sent to the outer cylinder of the ion exchanger 202.

pH
The adjustment fluid replenishment tank 61-6 is connected to the manifold 643 via a solenoid valve 634, and the water tank 617 is connected to the manifold 643 via a solenoid valve 639. and,
The manifold 643 is connected to the suction side of a metering pump 653 for replenishment. The discharge of the metering pump 653 for replenishment (11114, manifold: 642 is connected to one of the solenoid valves 631 to 635, and each solenoid valve is
It is connected to plating tanks 61 to 65.

Each item necessary for calibrating the pH meter, calibrating the atomic absorption photometer↓02, calibrating the ultraviolet absorption detector 203, measuring the pH of the plating solution, measuring the concentration of the reducing agent component in the plating solution, and measuring the concentration of the gold component in the plating solution. The operation.

This is carried out by the sequencer 50 according to a command from the arithmetic control means 40↓.

That is, solenoid valves 620 to 630, 671°673.6
81,682, metering pumps 651-658, three-way valve 650, six-way valve 660°662.664,666,
Sample loops 661, 663, 665, and 667 operate in sequence according to commands from sequencer 501.

A method for calibrating the measuring device and a method for measuring the concentration of the plating solution components will be described using FIG. 5 showing the flow of operations on the sequencer 50 and the arithmetic control means 4.01. In FIG. 5, the operations enclosed by a double frame are performed by the arithmetic control means 4.01, and the others are performed by the sequencer 501.

Calibration of the pH meter is performed as follows.

Solenoid ↑623, three-way Halpro 50, and six-way valve 660
After forming a flow path to feed the sample into the sample loop 661, the metering pump 65 is driven, and the buffer solution 4'F,
'612 containing thorium borate buffer (pH approx. 9)
．． 2) is collected into the sample loop 661. The metering pump 651- is driven for a certain period of time and then stopped, and the sodium borate IX buffer is poured into the flow cell 301.

The pH of the buffer solution is determined using a pH electrode 302 inserted into the flow cell 30.

After the p I-I measurement, the electromagnetic valve 620 is opened, the metering pump 65 is driven, and the p I-1 electrode cell and the like are cleaned.

The arithmetic and control means 40 stores in advance a permissible variation range for calibration values obtained through repeated preliminary experiments, and performs an abnormal value test on the obtained calibration values.

The permissible range is determined in advance through repeated preliminary experiments during which the calibration value fluctuates, and is set to an appropriate range.

Calibration of pH meter and ultraviolet absorption detector 2 described later
For calibration of 03, calibration of atomic absorption spectrometer 1.02, and concentration measurement of plating solution components, a pH meter 303 and a pH electrode 30 are used.
2. Immediately detect an abnormality in the atomic absorption photometer ↓02, ultraviolet absorption detector 203, decrease in ion exchange capacity of the ion exchanger, abnormality in each metering pump, liquid leakage in each piping system, generation of air bubbles in the middle of the piping, etc. Affects the calibration value of the measuring device and the measured concentration of the plating solution components.

If the calibration value falls outside the allowable range, which will be described later, an alarm is issued to notify the operator, and the operator is asked whether to perform the measurement again or to terminate the measurement. In this way, erroneous management based on erroneous measured values is prevented.

Calibration of the ultraviolet absorption photometer 669 is performed as follows.

9 In the same manner as described above, the reducing agent standard solution stored in the reducing agent standard solution 411611 is taken into the sample loop 661 and then sent to the dilution tank 670. By operating the metering pump 652 for a certain period of time, the water is transferred from the water tank 617 to the dilution tank 67.
0--A fixed amount of water is fed to dilute the reducing agent standard solution, for example, 50 times in the dilution tank 670. Metering pump 656
is driven to collect the diluted standard solution into the sample loop 667.

The double-layered standard solution passes through an ion exchange membrane tube 201 and is measured by an ultraviolet absorption detector 203 whose measurement wavelength is set to 240 nm.

A reducing agent standard solution diluted 50 times is sampled twice for measurement.

The arithmetic control means 4.01 calculates the average value of the two measurements and performs a value test.

The abnormal value test is performed using both the average value and the dispersion (absolute value of difference) of the values measured twice. If either the average value or the dispersion exceeds the predetermined manual tolerance range, an alarm will be issued to notify the operator and ask them to confirm whether they want to take the measurement again or end the measurement. Let's do it.

Therefore, in order to quickly discover abnormalities in these devices, the allowable range is set in advance to an appropriate range through repeated preliminary experiments.

Calibration of the atomic absorption photometer 102 is performed as follows.

The standard solution is a mixture of a metal component standard solution obtained by removing the reducing agent thiourea from the plating solution used in this example, and a reducing agent-added solution consisting of a thiourea solution.

The gold standard solution stored in the metal separation standard solution tank 610 is diluted, for example, 50 times, in the dilution tank 670 in the same manner as the standard solution for the ultraviolet absorption detector.

The metering pump 656 is driven to collect the two-layer diluted standard solution into the sample loop 665. At this time, the metering pump 654 is simultaneously driven to collect the thiourea solution from the reducing agent addition liquid tank 618 into the sample loop 663. Then, by switching the six-way valve 664 and the six-way valve 662 simultaneously, the thiourea solution in the sample loop 663 and the diluted standard solution in the sample loop pro 65 are simultaneously transferred to the dilution tank 67.
Send to 2.

Further, the mixed solution in the dilution tank 672 is diluted, for example, 100 times.

The concentration of the thiourea additive solution and the reducing agent additive solution in the standard solution are adjusted to have a composition ratio close to that of the plating solution control concentration.

” The standard solution obtained in the two-layer rectangular solution was
．． 01, and then measured using an atomic absorption spectrophotometer 102. The standard solution in the dilution tank 672 is sampled and measured again.

After the measurement, the solenoid valve 671. ．． 673 to discard the diluted sample, metering pumps 652 and 655 to send H2O,
The dilution tanks 670 and 672 are cleaned.

Further, the electromagnetic valve 620 is opened to drive the metering pump 651, and the piping system for collecting the standard solution is washed with water.

The arithmetic control means 4.01 calculates the average value of the two measurements, and performs an abnormal value test in the same manner as the abnormality test of the ultraviolet absorption detector described above.

If an abnormal value is measured, an alarm device sounds to notify the operator of the abnormality, and the operator confirms whether to take the measurement again or to end the measurement.

The pH meter 303, atomic absorption spectrophotometer 102, and ultraviolet absorption detector 203 are preferably rotated in the positive direction at least once a day.

Measurement of component concentration of plating solution and calculation of replenishment amount will be explained.

The pIT measurement of the plating solution is performed as follows.

A flow path is formed to feed into the sample loop 66↓ through the solenoid valve 626, three-way valve 650, and six-way valve 660, and the metering pump 651 is opened and, for example, the plating tank 1 is fed into the sample loop 66↓.
A portion of the plating solution is collected into the sample loop 66''. The metering pump 651 is stopped after anal movement for a certain period of time, and p
F (Measure the pH of the plating solution with the electrode 302. Then,
Clean the piping system.

The concentration of the reducing agent component in the plating solution is measured as follows.

The metering pump 652 is opened for a certain period of time to feed a certain amount of water from the water tank 34-617 to the dilution tank 670. During the process, the six-way valve 660 is switched, and the plating solution sample collected into the sample loop 661 via the solenoid valve 626, three-way valve 650, and six-way valve 660 is simultaneously fed into the dilution tank 670 and diluted 50 times.

Open the solenoid valve 681 and supply nitrogen gas to the dilution tank 670 for a short time.
to stir the liquid.

Six-way valves 664 and 6 are connected so that a portion of the 50-fold diluted sample in dilution tank 670 can be sent to sample loop 667.
66, the metering pump 656 is activated, and the diluted sample is sent to the sample loop 667.

A metering pump 657 is attached to the anion exchange membrane tube 201.
H2O is constantly supplied at a flow rate of 2 m11/min. Furthermore, by switching the six-way valve 666, the diluted sample collected in the sample loop 667 is sent to the anion exchange membrane tube 20↓.

Anion exchange membrane tube 201 of anion exchanger 202
A regenerating liquid tank 619 is supplied to the outside by a metering pump 658.
For example, a 0.2N anion solution stored in the tube is sent at a flow rate of, for example, 2 ml/min, and the anion exchange membrane tube 20↓ is constantly regenerated into a chloride ion form. When a plating solution sample is sent into this anion exchange membrane tube 201, sulfite ions, thiosulfate ions, and all complex ligands, etc. in the plating solution are captured on the anion exchange membrane and replaced with chlorine. Ions elute.

On the other hand, since the reducing agent thiourea is a nonionic substance, it is not captured within the anion exchange membrane tube 668 and is sent to the ultraviolet absorption detector 203 together with the eluted chlorine ions.

The measurement wavelength of the ultraviolet absorption detector 203 is set to 240 nm, at which thiourea exhibits absorption. Chlorine ion is 240
Since it shows no absorption at nm, the absorbance due to thiourea alone is measured.

The metering pump 657 is started again, and the sample loop 6
Collect a 50-fold diluted sample in a 67-mL container, repeat the same operation, and measure the absorbance twice.

The concentration of gold components in the plating solution is measured as follows.

The six-way valve 664 is connected to send the 50-fold diluted sample in the dilution tank 670 to the sample loop 665, and the constant pump 656 is driven to send the diluted sample to the sample loop 665.

The six-way valve 664 is switched to send the diluted sample in the sample loop 665 into the dilution tank 672 .

At the same time, the metering pump 655 is driven for a certain period of time to feed a certain amount of H2O into the dilution tank 672, thereby diluting it, for example, 100 times. Open the solenoid valve G82 and stir with nitrogen gas. A part of the two-stage diluted sample in the dilution tank 672 is sent to the atomic absorption spectrophotometer 02 by the autosampler 101-, and the total concentration is measured.

The autosampler 101 is operated again to sample the diluted solution and measure the total concentration.

After the measurement, the solenoid valves 671 and 673 are opened to discard the diluted sample, and the metering pumps 652 and 655 are used to send H2O to clean the dilution tanks 670 and 672. In addition, the electromagnetic valve 62
5 is opened to drive the metering pump 651, and the piping system for collecting the plating solution is washed with water.

The calculation control means 401 performs a proportional calculation between the average value of the total concentration of the plating solution and the reducing agent concentration obtained in the two measurements, and the average value of the calibration values obtained by repeating the measurement of the standard solution twice. 1
) to calculate the gold and thiourea concentrations in the plating solution.

Measured concentration value of the desired plating solution x standard solution concentration calibration value... (1) Even if there is a background in the measurement device, if the standard solution is at almost the same concentration as the target control concentration, the error in this vicinity is extremely small. .

Of course, the concentration measurement method is not limited to the two-layer method, and a calibration curve may be created using several types of standard solutions with different concentrations.

The calculation control means 40↓ verifies whether the calculated concentration and pH value of the plating solution are within the permissible range of the control concentration. If the value is outside the allowable range, an alarm is issued to notify the operator and the operator is asked whether to take the measurement again or to terminate the measurement.

In this way, erroneous management based on erroneous measured values is prevented.

Further, the arithmetic control means 40 calculates the amount of component consumption as plating progresses from the difference between the calculated concentration of the plating solution and the control concentration, and calculates the amount of replenishment. Since replenishment requires changing the opening/closing time of the solenoid valve and the opening/closing time of the pump depending on the amount of replenishment, the arithmetic control means 4.01 performs the control.

Metal component replenishment tank 614, reducing agent replenishment tank 6]-5
To replenish the plating solution tank, use Electromagnetic Halpro 3], ~63
5 is opened and the metering pump 653 is operated.

The replenishment time for gold and thiourea is calculated from the concentration of the gold and thiourea replenisher, the liquid volume in the plating tank, the flow rate of the metering pump 653, etc., and the solenoid valves 636 and 637 are sequentially opened for a predetermined time to obtain the required amount. refill.

To replenish the p Hm wave, open the solenoid valve 638 for a preset replenishment time according to the measured pH value of the plating solution.
Replenish H adjustment fluid.

After replenishing each replenisher, the solenoid valve 639 is opened for a certain period of time to wash the piping system with water.

Furthermore, the arithmetic control means of this embodiment includes the anion exchanger 2
Equipped with a program to check the ion exchange ability of 02.

If only the thiourea concentration in the plating solution exceeds the allowable range, the cause may be a decrease in the ion exchange capacity of the anion exchanger 202. At this time, the check can be performed by the following operation (automatically) depending on the operator's program selection.

This program selection is performed by the calculation control means 4. Instructions can be given from an input device such as a keyboard (not shown).

That is, the solenoid valve 624 is opened and the metering pump 651 is used to supply N.
Collect the a2S,,03 solution into the sample loop 661,
After diluting it in the dilution tank 670, the absorbance is measured using the ultraviolet absorption photometer 203 in the same manner as the thiourea concentration measurement.

If the ion exchange ability of the anion exchanger 202 is normal, the thiosulfate ions will be captured by the anion exchange membrane and the chlorine ions will be eluted instead, so the ultraviolet absorbance will be zero. However, if the anion exchange capacity decreases,
Since some or all of the thiosulfate ions are sent as they are to the ultraviolet absorption detector 203, they exhibit some kind of absorbance and can easily detect abnormalities.

Hereinafter, the effects of the embodiments described so far will be explained.

When a plating solution containing reducing ions such as sulfite ions and thiosulfate ions and total complexes with sulfate ions and thiosulfate ions as ligands is passed through an anion exchange membrane that has adsorbed chlorine ions, anion exchange occurs. Sulfite ions and thiosulfate ions, which have a high affinity for the substance, are captured by the anion exchange material, and an equivalent amount of chlorine ions are eluted instead.

In this way, the reducing ions contained in the plating solution are exchanged with anions that do not interfere with the quantitative analysis of the reducing agent contained in the plating solution. .

However, due to its ionic nature, thiourea is not captured by the lIλ ion exchange membrane and flows out from the anion exchanger as it is. Accurate measurements can be made with an ultraviolet absorption detector installed after the ion exchanger.

If the reducing agent is a substance that does not exhibit ultraviolet absorption, such as formaldehyde, a potentiometric titration device rather than an ultraviolet absorption detector can be used to calculate the concentration from the amount of current required to oxidize pol-11 aldehyde. can do.

At this time, the chloride ions do not interfere with the measurement. However, the concentration of the measurement solution is different from that when measuring the concentration of thiourea using an ultraviolet absorption detector.

In order to quantitatively analyze the gold component, an analyzer such as a plasma emission spectrometer may be used instead of the atomic absorption method.

However, in-shell plasma emission spectrometry requires a larger measuring device than atomic absorption spectrometry.

In particular, in the concentration control device of Example 3, a standard solution containing not only metal components but also a mixture of 1 2 metal components and reducing agent components is used as the standard solution for the atomic absorption spectrophotometer, and it is possible to detect Prevents fluctuations in measured values.

Furthermore, by mixing the metal component and the reducing agent component immediately before the 41 step, it is possible to prepare a standard 7 (Li solution) that does not undergo liquid decomposition and perform an accurate 1 step measurement.

pH measurement is carried out once a day, but may be carried out multiple times.

In this embodiment, the measurement and calibration by the measuring device are automated by controlling them using a sequencer, but instead of using a sequencer, arithmetic control means are used.
Measurement and calibration by the measuring device may be controlled.

The arithmetic control means takes in the measured value and the calibration value sent from the measuring device, and calculates the concentration according to the above-mentioned equation (1). From the difference between the determined concentration of the plating solution and the control concentration, the consumption amount of the component as plating progresses is determined and the replenishment amount is calculated. Then, the component concentration of the plating solution is always managed within a certain range by sequentially replenishing the consumed amount from the replenisher tank according to the information on the amount of consumed components. As a result, the plating speed can be kept constant.

Furthermore, the arithmetic control means performs an abnormality check on the measured value of the component concentration of the plating solution, and depending on the measured value, immediately performs re-measurement or checks the apparatus. Thus, i11'l &
(Make the direct I1F reliability the same.

Using the concentration control device of Example-3, the pH and the concentrations of gold and thiourea were measured every hour, and while replenishing the pH adjustment solution and the gold and thiourea replenishment solution, ], dm2/
Plating was carried out for about 20 hours under a load of Q.

At this time, the pH was 9 to 9.1, and the total concentration was ±5% of the control concentration.
Since the thiourea concentration could be automatically controlled within the range of ±3% of the control concentration, the plating rate could be adjusted within the range of 1.0 to 0.85 μm/hour.

Similar results were obtained with the concentration control device of Example-2.

As described above, the density control device of the present invention maintains the plating speed constant during the plating process, so that uniform plating can be performed without unevenness. That is, the concentration control device of this embodiment can be used as an excellent tampering device.

Furthermore, the concentration control device of the present invention can control the replenishment solution and the standard solution even in various plating solutions other than non-cyanide electroless plating solutions.
By appropriately changing the components of the plating solution used,
Therefore, it is possible to control the acidity of the liquid. Also,
Similarly, it can also be applied to non-cyanide electroless plating equipment.

The concentration control devices of Examples 2 and 3 use an atomic absorption spectrophotometer to analyze the concentration of the gold component, but it is also possible to provide a metal component concentration measuring means by selecting an analyzer suitable for the metal component to be measured. can. Similarly, although an ultraviolet absorption detector is used to analyze the concentration of the reducing agent component, it is possible to provide a nonmetallic component measuring means that can determine the concentration of nonmetallic components other than the reducing agent.

The arithmetic control means of the concentration control device equipped with a metal component measuring means and a non-metallic component measuring means such as a double layer is as described in the embodiment-
Arithmetic control means such as those described in 2 and 3 can be used.

For example, a concentration control device equipped with a polarograph as a means for measuring metal components and a liquid chromatograph as a means for measuring non-metal components can be connected not to a plating tank but to, for example, a waste liquid tank such as factory wastewater, so that metal components can be measured. The measuring means measures the concentration of, for example, cadmium, and the non-metal component measuring means measures, for example, the concentration of organic substances such as ketones, thereby making it possible to manage the water quality of factory wastewater. At this time, the standard solution and replenisher to be used are changed as appropriate depending on the metal components and non-metal components contained in the factory wastewater.

Furthermore, the concentration measuring method of the present invention can be used, for example, for water quality testing of rivers and the like.

(The following is a blank space.) 5 6- [Effects of the Invention] As explained in detail below, according to the method for measuring the component concentration of a plating solution of the present invention, anions coexisting in the plating solution can be used to measure the reducing agent. Since the concentration of the reducing agent can be measured by converting it into another anion species that does not cause interference, the concentration of the reducing agent in the plating solution can be measured with high precision.

Furthermore, if the equipment using the method described in -1- is equipped with a function to calculate the amount of plating solution consumed and replenish it, the component concentration of the plating solution can be always adjusted within a certain range. Automatic management can be achieved.

Further, the concentration management device of the present invention, which includes a metal I component concentration measurement section, a nonmetal component concentration measurement section, and an arithmetic control section, can measure the concentration of metal components and the concentration of nonmetal components in a solution. When each measured value is outside a predetermined tolerance range, the calculation control unit operates and adds the replenisher stored in the replenisher tank to bring the concentration of each component of the solution within the tolerance range. I can do it.

[Brief explanation of drawings]

FIG. 1 is a system diagram showing the configuration of an embodiment of the concentration measuring device used in the concentration measuring method of the present invention, and FIG. 2 shows thiourea,
An ultraviolet absorption spectrum diagram of urea and KCQ, FIG. 3 is a system diagram showing the configuration of an embodiment of the concentration adjustment device used for concentration adjustment of the present invention, and FIG. A system diagram showing an example of a plating apparatus that adjusts
Fig. 5 is a flowchart 1 to 1 showing the operation of the calculation control means used in the embodiment shown in Fig. 4, and Fig. 6 is a case in which plating is performed using a non-cyanide plating solution without adding a replenisher. Figure 7 is a graph showing changes over time in the components of plating. Figure 7 shows changes over time for one minute and changes over time in plating speed when plating is performed using a non-cyanide plating solution by adding replenisher as plating progresses. It is a graph. 7... Anion exchanger, 8 Anion exchange membrane tube, 9... Ultraviolet absorption detector,]]・Arithmetic control device, 11
...All standard solution tanks, 12. Thiourea standard solution tank, 13. Plating tank, 14.. All replenishment solution tanks, 15. Thiourea replenishment solution tank, 35.. Atomic absorption spectrophotometer, 610 Metal component standard solution. tank, 61]・Reducing agent standard solution tank, 612・-pT (buffer solution tank, 613 ”′ Na2S, 03 solution tank, 614 Metal component replenishment solution tank, 615・・Reducing agent replenishment solution tank, 616
・pH adjustment liquid replenishment liquid tank, 618... Reducing agent addition liquid tank, 61-9... Regeneration liquid tank, 101 Auto sampler, 1
02. Atomic absorption photometer, 201.. Anion exchange membrane tube, 202.. Anion exchanger, 203.. Ultraviolet absorption detector, 301 Flow cell, 302.. pH electrode,
303 pH meter, 4.01... Arithmetic control means.

Claims (12)

[Claims] 1. A method for measuring the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: replacing the anion with another anion species that does not interfere with the measurement of the concentration of the reducing agent; A method for measuring component concentration of a plating solution, which is characterized by measuring agent concentration. 2. A method for measuring the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: replacing the anion with another anion species that does not interfere with the measurement of the concentration of the reducing agent; A method for measuring the concentration of a component in a plating solution, comprising: measuring the concentration of the agent, and further measuring the concentration of the metal component by atomic absorption spectrometry or plasma emission spectrometry. 3. 3. The method for measuring the component concentration of a plating solution according to claim 1, wherein the reducing agent concentration is measured using an ultraviolet absorption detector or a potentiometric titration device. 4. A method for measuring component concentration of a plating solution containing metal components, reducing ions, and a nonionic reducing agent, the method comprising: replacing the reducing ions with non-ionic ions, and then measuring the concentration of the nonionic reducing agent. 1. A method for measuring component concentration of a plating solution, comprising: measuring and measuring the concentration of the metal component. 5. Measuring the metal component concentration in the plating solution and calibrating the metal component concentration measuring means used for this measurement; measuring the reducing agent concentration in the plating solution and calibrating the reducing agent concentration measuring means used for this measurement; The operation of replacing the anion with another anion species that does not interfere with the measurement of the concentration of the reducing agent is performed under sequence control according to a preset sequence program, and further, the measurement value obtained by the measurement and the A method for measuring the concentration of components in a plating solution, characterized in that the concentration of a metal component and the concentration of a reducing agent in the plating solution are determined by calculation from a calibration value obtained through calibration. 6. A method for adjusting the concentration of a plating solution containing a metal component, an anion, and a reducing agent, the method comprising: replacing the anion in the plating solution with another anion species that does not interfere with measurement of the concentration of the reducing agent; Calibration of the metal component concentration measuring means for measuring the component; Calibration of the reducing agent concentration measuring means for measuring the reducing agent component; Measurement of the metal component concentration by the metal component concentration measuring means; and Reducing agent concentration by the reducing agent concentration measuring means Calculate the consumption amount of the metal component concentration and reducing agent concentration using the calibration value and the measured value obtained from the concentration measurement, and then add a replenisher containing the reducing agent and metal component corresponding to the consumption amount. A method for adjusting the concentration of a plating solution, which comprises replenishing the plating solution. 7. An apparatus for adjusting the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, comprising: an ion exchange means for replacing the anion with an anion species that does not interfere with measurement of the concentration of the reducing agent; a regenerating means for regenerating the ion exchange means using a solution containing the reducing agent; a reducing agent concentration measuring means for measuring the reducing agent concentration; a metal component concentration measuring means for measuring the metal component concentration; a sequence control means for controlling calibration of the concentration measuring means and the metal component concentration measuring means; and measurement of plating solution components by the reducing agent concentration measuring means and the metal component concentration measuring means; From the value and the calibration value obtained by the calibration,
1. A component concentration measuring device for a plating solution, comprising a calculation control means for calculating a metal component concentration and a reducing agent concentration in the plating solution. 8. An apparatus for adjusting the component concentration of a plating solution containing a metal component, an anion, and a reducing agent, comprising: an ion exchange means for replacing the anion with an anion species that does not interfere with measurement of the concentration of the reducing agent; a regenerating means for regenerating the ion exchange means using a solution containing the reducing agent; a reducing agent concentration measuring means for measuring the reducing agent concentration; a metal component concentration measuring means for measuring the metal component concentration; a sequence control means for controlling the operations of the concentration measuring means and the metal component concentration measuring means; determining the consumption of the reducing agent and the metal component from the difference between the measured values of the reducing agent concentration and the metal component concentration and their respective set concentrations; Components of a plating solution, characterized in that it has a calculation means for calculating the consumption amount, and an arithmetic control means equipped with a supply means for supplying a replenisher containing a reducing agent and a metal component corresponding to the consumption amount to a plating tank. Concentration adjustment device. 9. A plating apparatus that performs plating using a plating solution containing a metal component, an anion, and a reducing agent, the plating apparatus comprising a plating tank, a plating solution concentration measuring means,
The plating solution concentration measuring means includes a plating solution replenishing means, a sequence control means, and an arithmetic control means; comprising a reducing agent concentration measuring means for measuring agent concentration and a metal concentration measuring means for measuring the metal component concentration, the sequence control means controlling the operation of the plating solution concentration measuring means, and the calculation control means , calculation means for calculating the consumption amount of the reducing agent and the metal component from the difference between the measured values of the reducing agent concentration and the metal component concentration and the respective set concentrations, and the reducing agent and the metal component corresponding to the consumption amount. A plating apparatus comprising a supply means for supplying a replenisher from the plating solution replenisher to a plating tank. 10. A metal component concentration measuring means for measuring the concentration of a metal component contained in a solution, and a non-metal component concentration measuring means for measuring a non-metal component concentration, further comprising: the metal component concentration measuring means and the non-metal component concentration. A control function that controls the operation of the measuring means, and a metal that corresponds to the consumption amount of the metal component and the non-metal component based on the difference between the measured values of the concentration of the metal component and the concentration of the non-metal component and the respective set concentrations. What is claimed is: 1. A concentration control device comprising: a replenisher containing a component; and a supply function for supplying a replenisher containing a non-metallic component. 11. 11. The concentration control device according to claim 10, wherein the metal component concentration measuring means is an atomic absorption spectrophotometer or a plasma emission spectrophotometer. 12. 12. The concentration control device according to claim 10, wherein the nonmetal concentration measuring means includes an anion exchanger, and an ultraviolet absorption detector or a potentiometric titration device.