KR20040034464A - Method and apparatus for maintaing an eching solution - Google Patents

Abstract

PURPOSE: Provided are a method and an apparatus for controlling an etching solution for use in metal type materials, which maintain the concentration of each component varying with the lapse of time at a substantially constant value. CONSTITUTION: The method for controlling the concentration of each component in an etching solution for use in metal type materials(10) repeatedly, comprises the steps of: titrating the etching solution with a solution having a nature opposite to that of the etching solution, while measuring the electroconductivity of the etching solution; calculating the amount of a component deficient in the etching solution by using the measured value; and providing the etching solution with the amount of the deficient component as calculated above by using parent liquor of the component and/or a supplementary solution.

Description

Etching solution management method and etching solution management device {Method and apparatus for maintaing an eching solution}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for managing an etchant and a management apparatus thereof, and more particularly to a method for managing an etchant and a device for managing the etchant for maintaining a substantially constant component concentration of an etchant for a metal material used repeatedly.

Background Art Conventionally, a processing method called etching has been used, for example, for processing printed circuit boards, ITO films, lead frames, and the like, and for fine steel processing for polishing the surface of steel. Specifically, a metal thin film pattern is formed by using an etching solution on a substrate of an array substrate constituting a flat panel display device such as a liquid crystal display and an organic EL display and on a base of a silicon wafer constituting a semiconductor element.

Etchants generally consist of water and some volatile components. Their components depend on the metal to be etched. For example, in the case of liquid crystal displays, the metal thin film on the substrate is composed of an aluminum-based metal thin film having high conductivity and a high melting point metal film such as molybdenum. In this case, a metal thin film pattern is formed using an etchant in which nitric acid, acetic acid, phosphoric acid and water are mixed at a predetermined ratio (see Japanese Patent Application Laid-Open No. 2001-77085).

In the etching process, the etchant is used, for example, by spraying a shower onto the substrate or by dipping the substrate into the etchant. In addition, the etching liquid is generally used repeatedly in this process in order to process a some board | substrate. However, the etching liquid used repeatedly changes its component composition over time, such as by carrying out by a board | substrate, misting at the time of spraying, and evaporation. As a result, there arises a problem that a sufficient etching effect is not obtained at the same time as time passes.

In addition, the etching liquid causing the change in the component composition needs to be frequently exchanged, and the used etching liquid needs to be discarded, resulting in a large cost.

For example, Japanese Patent No. 2747647 discloses an etching liquid discharge means for detecting a dissolved indium concentration of an etching liquid for a transparent conductive film by using an absorbance photometer and discharging the etching liquid, and detecting the liquid level of the etching liquid by using a liquid level level meter. A first supply means for replenishing and a second supply means for replenishing an etching stock solution or pure water by detecting an acid concentration of the etchant using a conductivity meter are disclosed. This apparatus measures the dissolved metal concentration in the etching solution using an absorbance photometer, and measures a single acid concentration using a conductivity meter. The etching rate is maintained by replenishing the acid or pure water in the etching liquid based on the measurement result. However, in the invention described in Japanese Patent No. 2747647, it is difficult to manage the component concentration of the etching solution composed of a plurality of components.

For example, Japanese Patent Application Laid-Open No. 11-309403, Japanese Patent Laid-Open No. 11-309404, Japanese Patent Laid-Open No. 2000-119874, Japanese Patent Laid-Open No. 2000-199084, and a spinner are used to provide an etching solution to a substrate. The carry-out of the etching liquid to the outside of the coating apparatus and the loss by misting are prevented. However, it is still not possible to cope with a change in concentration due to evaporation of the etching solution.

An object of the present invention is to easily and substantially maintain a constant component concentration at which the etching solution for metal-like materials used repeatedly changes over time.

1 is a schematic view showing one embodiment of an etchant management apparatus.

2 is a schematic diagram showing an example of titration and measurement means.

FIG. 3 is a graph showing the titration line of the etching solution represented by the addition amount and the conductivity of the reverse solution. FIG.

4 is a schematic diagram showing another example of the titration / measurement means.

* Description of the symbols for the main parts of the drawings *

10: metal material 100: etching solution management device

101: etching bath 102: shower nozzle

103: recovery pipe 104: storage and recovery tank

104a: pipeline 104p: pump

105: stock solution / supplement liquid storage tank 105a: pipeline

105b: flow control valve 105p: pump

106: pipeline 106b: on-off valve

106p: pump 107: discharge pipe

107b: discharge valve 108b: discharge valve

109: pipeline 109b: on-off valve

110: calculation means 200: titration / measurement means

201: reaction vessel 202: stirring device

203: conductivity meter 204: backwash tank

204a: Pipe line 205: Backwash solution tank

205a: pipeline 209: pure water introduction tube

210: weighing syringe

In one aspect, the present invention relates to a management method for maintaining a substantially constant component concentration of an etchant for metal-like materials used repeatedly. This method uses a titration / measurement step of titrating the etchant using a solution inversely related to the etchant and measuring the electrical conductivity of the etchant in parallel thereto, and using measurement values obtained by the titration / measurement step. And a replenishment step of replenishing the deficient component amount in the etchant and supplying the deficient component amount calculated by the calculation step to the etchant using a component stock solution and / or a replenishment solution.

The etching solution may be an acid solution. The acidic solution may contain at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, cyanic acid, dicerium ammonia, ammonium persulfate and ammonium chloride.

The etching solution may be an alkaline solution. The alkaline solution may contain at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium bichromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate.

The inverted solution may be an acid solution. The acidic solution may contain at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, cyanic acid, dicerium cyanate, ammonium persulfate and ammonium chloride.

The inverted solution may be an alkaline solution. The alkaline solution may contain at least one member selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium dichromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate.

In the titration / measurement step, the etching solution may be titrated by a quantitative dispensing method using the inverted solution.

In the replenishment step, the amount of the insufficient component may be replenished in the etching solution using the replenishment liquid determined by the following formula (I).

d = ΣdNn ... Formula (I)

Wherein d is the replenishment weight, N is the component contained in the etchant, dN is the deficiency weight of the N component with respect to the etchant, and n represents an integer of 1 or more.

In another aspect, the present invention relates to a management apparatus for maintaining a substantially constant component concentration of an etchant for metal-like materials used repeatedly. The apparatus uses a titration / measurement means for titrating the etchant using a solution inversely related to the etchant and measuring the electrical conductivity of the etchant in parallel thereto, and a measurement value obtained by the titration and measurement means. And at least a replenishment means for replenishing the deficient component amount in the etchant and the depleted component amount calculated by the arithmetic means to the etchant using a component stock solution and / or a replenishment solution.

(Example of the invention)

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described in detail, referring an accompanying drawing. This embodiment is only an example of the present invention, and the present invention is not limited thereto. In addition, in description of drawing, the same code | symbol is attached | subjected to the same element, and the overlapping description is abbreviate | omitted.

1 is a schematic diagram showing the apparatus 100 of this embodiment. The apparatus 100 includes an etching bath 101, a recovery pipe 103, a storage / recovery tank 104 for etching liquid, a titration / measurement means 200, a calculation means 110, a stock solution / replenishment storage tank 105, And pipes for connecting these devices. The etching bath 101 contains the shower nozzle 102 and etches the metallic material 10 to be etched. The recovery pipe line 103 recovers the used etchant in the etching bath 101.

In the etching bath 101, the metallic material 10 to be etched is etched by the etching liquid injected from the shower nozzle 102. In addition, although the etching apparatus of a shower nozzle type is demonstrated in this specification, the immersion type etching apparatus may be used instead.

As used herein, the term "metal-type material" includes metals such as lithium, aluminum, titanium, iron, copper, molybdenum and silver, and oxides and nitrides thereof and elements such as silicon, fluorine, arsenic, selenium and tellurium. Oxides and nitrides. In most cases, aluminum, silver and molybdenum, which are generally used as wiring materials, are used as metal type materials, but are not limited to these.

As etching liquid used by this invention, an acidic solution and an alkaline solution are mentioned, for example. The acidic solution includes, for example, at least one selected from the group consisting of acids such as nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid and cyanic acid, and acid salts such as dicerium nitrate, ammonium persulfate and ammonium chloride. It is preferable that 1 type is contained. On the other hand, the alkaline solution contains, for example, at least one selected from the group consisting of hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide, and alkaline salts such as potassium dichromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate. It is preferable that paper is contained. Which one of these etching solutions is used can be appropriately selected by those skilled in the art according to the type of metal-like material 10 that is the object of etching.

Since the etching liquid used in the etching tank 101 is used repeatedly, it collect | recovers to the storage and collection tank 104 once. The component concentration of the etchant used repeatedly is carried out to the outside of the apparatus attached to the etched metal-like material 10, misting by spraying the etchant, evaporation by the temperature rise in the etching bath 101, and the etched metal. It changes with time because of the influence from the component of the mold material 10, etc. When the etching liquid which changed the component concentration is used, maintenance of an etching rate will become difficult.

The apparatus 100 is equipped with the titration / measuring means 200 as shown in FIG. The titration / measurement means 200 passes through the sample introduction pipe 109 to the reaction vessel 201 where the etching solution is introduced from the storage / recovery tank 104, a metering syringe 210 for quantitatively introducing the etching solution, and pure water. Reverse solution tanks 204 and 205 for storing a pure water introduction pipe 209 introduced into the reaction vessel 201 and a solution having a reverse performance with the etching solution (hereinafter referred to as "reverse solution" in the present specification), and reaction. It consists of the stirring apparatus 202 which stirs the etching liquid in the container 201, and the conductivity meter 203 etc. which measure the electrical conductivity of the etching liquid in the reaction container 201.

In the present specification, the "reverse solution with an etching solution (reverse solution)" means an alkaline solution when the etching solution is an acid solution, and an acid solution when the etching solution is an alkaline solution.

The reverse solution used in the present invention includes, for example, hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide and potassium chromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate when the etching solution is an acidic solution. It is preferable that at least 1 sort (s) chosen from the group which consists of alkaline salts is contained. On the other hand, when the etching solution is an alkaline solution, the reverse solution includes, for example, acids such as nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid and cyanic acid, and dicerium nitrate, ammonium persulfate and ammonium chloride; It is preferable that at least 1 sort (s) chosen from the group which consists of the same acid salt is contained. Whether to use these inverse solutions can be appropriately selected by those skilled in the art according to the components contained in the etching liquid to be titrated.

In the present invention, "titration" refers to a so-called "neutralization titration". Hereinafter, the titration process of etching liquid is demonstrated using PAN (mixed solution of phosphoric acid, acetic acid, and nitric acid) which is an etching solution generally used for etching of aluminum, and NaOH (sodium hydroxide) solution which is its reverse solution as an example.

Pure water is introduced into the reaction vessel 201 washed with pure water through the pure water introduction pipe 209 until the sensor portion of the conductivity meter 203 is immersed in the liquid. After discharging the remaining liquid in the sample introduction tube 109, about 1 ml of etching liquid was measured using the metering syringe 210, the etching liquid was introduced into the reaction vessel 201, and the reaction vessel 201 was stirred in the stirring apparatus 202. The liquid in the inside is made uniform. Thereafter, the electrical conductivity of the etchant diluted with pure water in the reaction vessel 201 is measured using the conductivity meter 203. The 0.1 N NaOH solution is stored in advance in the inverted solution tank 204, and a predetermined amount (for example, 1 ml each) or an appropriate known amount is introduced into the reaction vessel 201, and the electric conductivity is stirred after stirring. Measure it. If the concentration difference between the components (phosphoric acid, acetic acid and nitric acid) in the etching solution is large, a 1 N NaOH solution prepared in advance in the reverse solution tank 205 is introduced into the reaction vessel 201 in the same manner as the 0.1 N NaOH solution. Measure the conductivity.

When the amount of introduction of the 1 prescribed NaOH solution is taken on the horizontal axis and the electrical conductivity (conductivity) is taken on the vertical axis, the graph shown in FIG. 3 becomes the same. The solid line in FIG. 3 shows the trend of the actual measured value by the conductivity meter 203. The titration proceeds from acid with strong acid. In this example, the process proceeds from nitric acid in the etching solution. The line from the left end of the graph of FIG. 3 to P1 is the titration line for nitric acid, the line from P1 to P2 is the titration line for acetic acid, and the line from P2 to P3 is the titration line for phosphoric acid. . P1, P2, and P3 in contact with the intersection of the titration line are the titration points of the respective acid components. The relationship between the amount of NaOH solution introduced and these appropriate points indicates the concentration of the component of the etchant that changes at that time.

For example, when a small amount of components in the etching solution and the NaOH solution or the like are difficult to titrate in a general alkaline solution, an alkaline solution such as an aqueous solution containing Na salts derived from the acid component to be measured is used as a reverse solution (titration solution). When used, the bending points (for example, P1, P2 and P3) on the titration line appear more remarkably.

After completion of the measurement, the liquid in the reaction vessel 201 is discharged through the discharge pipe 107, and the reaction container 201 is washed with pure water introduced from the pure water inlet pipe 209.

As described above, the concentration of the plural components contained in the etching solution can be easily measured.

The calculating means 110 calculates the amount of replenishment components to be supplied to the storage / recovery tank 104 by using the component concentration of the etching liquid in the storage / recovery tank 104 measured by the titration / measuring means 200. . Examples of the computing means 110 include personal computers, workstations, and sequencers. These are appropriately selected by those skilled in the art. In accordance with the instruction from the computing means 110, the stock solution and / or the replenishment liquid of the required amount are supplied from the stock solution / replenishment tank 105 to the storage / recovery tank 104.

In this embodiment, the storage / recovery tank 104 is replenished using a replenishment liquid obtained by mixing the stock solution of the component contained in the etchant and / or the component contained in the etchant at a desired blending ratio. When more than one stock solution and / or replenishment solution are required, a plurality of stock solution / replenisher tanks 105 may be provided (not shown).

The weight of the replenishment liquid to be replenished to the storage / recovery tank 104 is derived according to the following formula (I).

d = ΣdNn ... Formula (I)

Here, d is the refill liquid weight, N is a component contained in the etching liquid, dN is the deficiency weight of the N component with respect to etching liquid, and n represents an integer of 1 or more. The weight d (formula (I)) to be replenished in the storage / recovery tank 104 is derived as follows.

Etching liquid is reduced by etching liquid mist generated at the time of etching, exhaust of etching liquid vapor, and carrying out of etching liquid by the metallic material 10 to the outside of the etching tank 101. FIG. In order to keep the concentration of the components of the etching solution almost constant, this loss may be supplemented with a replenishment liquid. Here, the components contained in the etching solution are referred to as N1, N2, N3, ... Nn. In addition, the weight of the etchant used during the etching of the metallic material 10 in akg, the exhaust weight of the etching liquid in bkg (sum of the etching liquid mist ikg and the etching liquid vapor vkg), and the weight of the etching liquid carried out by the metallic material 10 In ckg and the weight of the replenishment in dkg,

a-b-c + d = a, b = i + v, d = b + c and d = i + v + c.

Here, the weight resin of the component (N) contained in the etching liquid

aN-bN-cN + dN = aN, bN = iN + vN, dN = bN + cN, dN = iN + vN + cN

I think it's in the same relationship.

It is thought that the content rate of the component (N) contained in etching liquid mist and the etching liquid carried out by the metallic material 10 does not differ from the content rate of the component (N) contained in an original etching liquid. This is because they are physically taken out without accompanying chemical reactions. However, the content ratio of the component (N) contained in the etching liquid carried out to the outside by evaporation and the content ratio of the component (N) contained in the original etching liquid are considered to be different. This is because the vapor pressure varies depending on the components.

The weight (vN) of the component (N) carried out by the steam is

vN = WN / ΣW = WmN × pN / ΣW = WmN × (mN / M) × PN / ΣW. Where PN is the component vapor pressure at room temperature of the etchant, pN is the component vapor pressure, mN / M is the component mol fraction of the etchant, mN is the component mol concentration, M is the total component mol concentration, and WmN is the molecular weight of the component And WN represents the evaporable amount of the component.

From this fact, the weight d of the replenishment liquid to be replenished to the storage / recovery tank 104 is

d = dN1 + dN2 + dN3 + ... dNn = ΣdNn ... Formula (I).

When the stock solution of each component contained in the etching liquid is replenished to the storage / recovery tank 104, the replenishment amount of each component is derived based on the above dN.

Next, the control function of the apparatus 100 shown in FIG. 1 will be described. In the dry bath in which the storage / recovery tank 104 is empty, the opening / closing valve 106b opens, the pump 106p is operated, and the etching liquid is supplied to the storage / recovery tank 104 via the conduit 106. When the storage and collection tank 104 is filled with the etching liquid, the opening / closing valve 106b is closed, the pump 106p is stopped, and the supply of the etching liquid is stopped.

The metal material 10 is conveyed to the etching tank 101 by a conveying apparatus. The pump 104p is operated and the etching liquid is fed from the storage and recovery tank 104 to the etching tank 101 through the pipe line 104a. The etching liquid supplied to the etching tank 101 is shower-sprayed from the shower nozzle 102 to the metallic material 10 which is conveyed in the etching tank 101. The etchant sprayed onto the metal-like material 10 etches the surface of the metal-like material 10, a part of which is carried out of the etching bath 101 by the metal-type material 10, and another part is shown as a mist. It is discharged to the outside from the duct that does not. Another part evaporates and is discharged out of the duct. Most of the etching liquid is recovered to the storage / recovery tank 104 through the recovery pipe 103.

The concentration of the component of the etching liquid recovered in the storage / recovery tank 104 is changed by evaporation of a part of the above. As the etching operation of the metal material 10 proceeds, the component concentration of the etching liquid in the storage and recovery tank 104 changes.

When the on-off valve 109b opens, the etching liquid whose component concentration changed is supplied to the titration / measurement means 200 through the conduit 109. When the amount of etching liquid required for titration and measurement is supplied, the opening / closing valve 109b is closed. The measurement result of the titration / measurement means 200 is sent to the calculation means 110. The calculating means 110 returns the component concentration of the etching liquid in the storage / recovery tank 104 to an initial value, and calculates the weight of the component stock solution and / or replenishment liquid necessary for maintaining substantially constant. The calculating means 110 sends an electric signal to the flow regulating valve 105b and the pump 105b according to the result of the calculation, and the flow regulating valve so that the appropriate amount of the component stock solution and / or the replenishing liquid is supplied to the storage / recovery tank 104. 105b and the pump 105b are controlled. As a result, an appropriate amount of the component stock solution and / or replenishment liquid is supplied from the stock solution / supplement liquid storage tank 105 to the storage / recovery tank 104.

The control function of the titration / measurement means 200 shown in FIG. 2 will be described. Pure water is introduced into the reaction vessel 201 from the pure water introduction pipe 209 to the extent that the sensor portion of the conductivity meter 203 is submerged. The etching liquid of the quantity required for titration and measurement is supplied from the storage / recovery tank 104 to the metering syringe 210 via the conduit 109. By using the metering syringe 210, the appropriate amount of etching liquid required for titration and measurement can be metered. The etching liquid whose component concentration has changed is metered by the metering syringe 210 and fed to the reaction vessel 201. At this time, the stirring apparatus 202 is operated to make the solution concentration in the reaction vessel 201 uniform.

A predetermined weight of reverse solution is supplied from the reverse solution tank 204 or 205 to the reaction vessel 201 through the conduits 204a or 205a. The weight of the retrograde solution supplied is determined according to the kind of component which comprises an etching liquid. In the meantime, the advanced state of the etching liquid is measured by the conductivity meter 203. This measurement result is in turn sent to the calculation means 110.

When the titration is finished, the solution in the reaction vessel 201 is discharged from the conduit 107. Thereafter, pure water is introduced into the reaction vessel 201 from the pure water introduction tube 209, and the inside of the reaction vessel 201 is washed.

In this way, the component concentration of the etching liquid in the storage and collection tank 104 can be kept substantially constant.

In the above, this invention was demonstrated in detail based on the Example. However, the present invention is not limited to the above embodiment. Various modifications are possible in this invention in the range which does not deviate from the summary.

For example, the titration / measuring means 220 shown in FIG. 4 may be used instead of the titration / measurement means 200 described above. The titration / measuring means 220 differs from the titration / measurement means 200 in that the spectrophotometer 222 and the decolorization processing apparatus 224 are provided in the pipeline 109. The other structure of the titration / measurement means 220 is the same as that of the titration / measurement means 200. In addition, the spectrophotometer 222 may be arrange | positioned in the etching tank circulation line. In addition, the decoloring apparatus 224 is disposed upstream of the spectrophotometer 222.

The spectrophotometer 222 measures the spectral absorption intensity of the etchant sent from the storage and recovery tank 104 through the conduit 109. The decoloring apparatus 224 performs decolorizing treatment on the etching liquid before spectroscopic measurement. Decolorization of the etching solution is possible by subjecting the etching solution to at least one or more of heating, degassing, bubbling, and pressing.

The measurement value acquired by the spectrophotometer 222 is sent to the calculating means 110. The calculating means 110 calculates the component concentration of the etching liquid using this measured value, and calculates the amount of insufficient components in the etching liquid using the calculated component concentration. When the spectroscopic side can measure the component concentration of the etching solution more accurately than the titration using the conductivity meter, the calculating means 110 may supply the etching liquid in accordance with the amount of the insufficient component in the etching solution calculated using the measured value of the spectrophotometer.

According to the present invention, it is possible to easily and substantially maintain a constant component concentration at which the etching liquid for metal-like materials used repeatedly changes over time. Moreover, according to this invention, it becomes possible to keep the component concentration of the etching liquid containing a some component substantially constant. Moreover, in this invention, since the component which changes over time in an etching liquid is appropriately supplemented, the cost required for exchange and disposal of etching liquid can be reduced significantly.

Claims (12)

In the management method for maintaining substantially constant component concentration of the etching liquid for metal type materials used repeatedly, A titration / measurement step of titrating the etchant using a solution inverse to the etchant, and measuring the electrical conductivity of the etchant in parallel thereto; An arithmetic step of calculating the insufficient component amount in the etching liquid by using the measured value obtained by the titration and measurement step; And a replenishment step of replenishing the insufficient component amount calculated by the calculation step to the etchant using a component stock solution and / or a replenishment solution. The method of claim 1, wherein the etching solution is an acid solution. The method of claim 1, wherein the acidic solution is at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, cyanic acid, dicerium ammonium nitrate, ammonium persulfate, and ammonium chloride. Method containing species. The method of claim 1, wherein the etching solution is an alkaline solution. The method according to claim 4, wherein the alkaline solution contains at least one member selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium bichromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate. The method of claim 1, wherein the reverse solution is an acid solution. 7. The method of claim 6, wherein the acidic solution is at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, cyanic acid, cerium ammonium dinitrate, ammonium persulfate, and ammonium chloride. Containing The method of claim 1, wherein the inverting solution is an alkaline solution. The method according to claim 8, wherein the alkaline solution contains at least one member selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium bichromate, potassium ferricyanide, potassium cyanide, sodium carbonate and potassium acetate. The said titration and measurement process is a method of titrating the said etching liquid in the quantitative dispensing method using the said reverse solution. 2. The replenishment step according to claim 1, wherein the replenishment step replenishes the deficiency amount in the etching solution using the replenishment liquid determined by the formula d = ΣdNn, Wherein d is the replenishment weight, N is the component contained in the etchant, dN is the deficiency weight of the N component with respect to the etchant, and n is an integer of 1 or more. In the management apparatus for maintaining substantially constant component concentration of the etching liquid for metal type materials used repeatedly, Titration / measurement means for titrating the etchant using a solution inverse to the etchant, and measuring the electrical conductivity of the etchant in parallel thereto; Arithmetic means for calculating the amount of insufficient components in said etching liquid using the measured value obtained by said titration / measurement means, Etching liquid management apparatus provided with the supply means which replenishes the said insufficient component amount calculated by the said calculating means to the said etching liquid using a component stock solution and / or a supplement liquid.