TW554078B - Method for manufacturing metallic foil - Google Patents

Abstract

This invention is to reduce the consumption of an electrode coating in a method of manufacturing metallic foil by electrolysis from a sulfuric acid acidic solution using an anode having the coating containing a platinum group metal or metal oxide. In the method of manufacturing metallic foil by electrolysis from a sulfuric acid acidic solution, by adding a lead carbonate into the sulfuric acid acidic solution of electrolyte while using the anode having the coating of a platinum group metal or platinum group metal oxide, electrolysis is performed in the state of maintaining the lead concentration in the electrolyte at >= 10 ppm.

Description

554078 V. Description of the invention (1) [Detailed description of the invention] [Development: Technical field to which it belongs] The second Γ relates to a continuous manufacturing method of copper metal y used in printed circuit wiring boards and the like. [Previous technology] Manufacturing: The manufacturing method 'matches its material or use, and there are various methods of manufacturing, rolling, and electrolyzing using metal compounds ::: Electrolysis to facilitate plating on the cathode. / 'It is a representative metal foil produced by electrolysis: Almost all copper foils used on Γ3 are borrowed from cheap steel scraps as secondary materials. Even if the unprecipitated ingredients are not used, Transfer to a copper flute with a small amount of copper precipitation potential. Therefore, it is also possible to obtain impure materials with uniform thickness, and it is easy to obtain a wide area, which is suitable for the purpose of forming electronic circuits; ^ is a characteristic of tissue carving. Erosion of Easy-to-Lamp Large Longitudinal Ratio Figure 1 is a diagram illustrating an example of copper manufactured by electrolysis. As shown in the sectional view of Fig. I, a certain arrangement of 2 is that in the electrolytic bath 3 in the electrolytic cell 2, the main cathode 4 is manufactured as a cathode cylinder 4 to be insoluble; \ 2d-code \ 90-10 \ 90118853.ptd Page 4 554078 V. Description of the invention (2) Circle; 4 sides make / Λ belong to the continuous power ore on the surface of the cylinder,-the side is the surface of the cathode 冋The method of continuously stripping out the precipitated metallic copper 7; Obtaining two: the current value of C or the rotation speed of the cylinder 'makes it easy to control the average thickness of the copper 8; it has the characteristics of being easy to manufacture thin foil. The degree of lead electrode is usually 10 to several. In the past, women's products, i ^, and 5 gold electrodes were used as anodes. However, due to the consumption of anodes, the distance between the anode and the cathode cylinder is not good. , The electrolytic voltage will be increased, and it will also affect the obtained M as a positive s: i. Therefore, it has evolved to use an insoluble metal electrode == a substrate that is covered with an electrode catalyst material containing a metal of the original group or a metal lice. However, 疋, in the case of using platinum group metal or platinum group metal oxides, which is unfortunately t ㈣ as the anode), compared with the field ㉟ electrode ^, P makes 疋 can greatly extend the anode life = With this anode ..., a manufacturing method of a metal plutonium that can reduce the amount of insoluble metal and can be used for a long time is required. [Problems to be Solved by the Invention] The genus ❸ 'is used for producing gold such as electrolytic copper foil by electrolysis. ^ ^ Using a platinum group metal or a platinum group metal oxide genus :: ΐ mmetal electrode ㉟' Electrolytic manufacturing of metal poises that remain stable over a long period of time. [Means for solving problems] The following manufacturing methods can be used to solve the problems of the present invention: a kind of page 5 \\ 312 \ 2d-code \ 90-10 \ 90118853.ptd 554078 V. Description of the invention (3) Borrow f The method for manufacturing metal foil by electrolysis is in the method of manufacturing Jinmeixuan Group A metal negative from a sulfuric acid acid solution, by using a platinum group metal or platinum dioxo ::: coated anode 'and electrolyzing The sulphuric acid acid solution of the liquid is more than bismuth, in order to: perform the electrolysis while maintaining the wrong concentration in the electrolyte. Affiliation: Outer system: 金 Gold in the manufacturing method of manufacturing metal boxes by electrolysis [Embodiment of the invention] In the manufacture of metal pigs by electrolysis, due to the presence of insoluble m or fluoride ions, etc. Will cause the consumption of active coatings of the present inventors to increase. The following methods are recommended; a method of forming a stable == by "active coating h" method of forming metal foil on the electrode. After the coating of °, at the same time, electrolytic production; and in the production of metal foil, the number of production lines is PPm to Concentrations up to several tens of ppm: 2 = continuous characteristics' Therefore, additives such as urea and cellulose >, bone glue, sulfur, any of the above-mentioned additions are known: whether it is an electrode active material of a metal oxide It is an anode and contains a platinum group life. In the electrolytic treatment, the consumption of the anode is reduced, and the anode is reduced to alleviate the adverse effects of additives such as this. Lead concentration becomes 2 binary value == fruit, therefore, it is necessary to make \\ 312 \ 2d-code \ 90-10 \ 90118853.ptd page 6 554078 V. Description of the invention (4) The inventor is concerned with lead concentration At the time of the review, the agency learned that at 8 pPm lead concentration, the anode life could not be extended: it must be at least 10 ppm or more. Fruit gold 0 range: In order to dissolve the errors introduced from the raw materials, the electrolyte Metal or various lead compounds Lead in the electrolyte: Denier f ': There is a problem that the so-called error in the electrolyte is limited due to the root solubility product in the electrolyte. When reviewing the sulfuric acid = solution: concentration of the wrong component The hair concentration in the bath is not easy to rise to a concentration of about several ppm, and a concentration of about 7 to 8 ppm is the limit. Therefore: the inventors can improve the lead in the electrolyte: two = over A method that can stably maintain the concentration of the wrong component over a long period of time. At the time of inspection, it was found that although the sulfuric acid / liquid solution, the yttrium solution, lead dioxide, lead sulfate, etc. In some cases, even if the temperature changes from time to time, the concentration cannot be stably maintained over a long period of time. However, in the state of using lead carbonate, the concentration of the lead component can be stably maintained at 10 ρρπι or more. As the carbon salt of gold α, carbonic acid (), oxidized lead carbonate (2PbC03 · Pb (〇H) 2), etc. can be used. In sulfuric acid-based electrolyte, carbon dioxide is produced. Dissolve; Although there is no reason to increase the lead concentration, > 疋 a speculate 疋 = the dissolution process of lead carbonate dissolved in sulfuric acid acid bath, to play a role in improving the lead concentration in the electrolyte. In the present invention In the lead carbonate to be added to the electrolyte,

554078

Warm 100 g / l of dilute sulfuric acid to 60 ° C. The solution was taken every day and the membrane was passed through the membrane: ^ carbon: ，, using an inductive plasma luminescence spectroscopy device ^ d j and quantitative lead concentration. ^ Yang Dao Qi

The results of Example 1 and the results of Comparative Example 丨 are shown in Table 1 _ Example 2 Copper foil electrolyte at a copper concentration of 80 g / l, a sulfuric acid concentration of 95 g // 1, a lead concentration, and a gelatin concentration of 10 ppm. In a copper dissolving tank, lead carbonate was added, in which the oblique weight was 0.2 g per liter of electrolyte in terms of miscellaneous weight. The electrolytic cell, as shown in Figure 1, is equipped with two anodes. The two anodes are for a titanium cylindrical cathode with a diameter of 2 m, the distance between the electrodes is set to 10 mm, and the arc-shaped titanium plate is used. An electrode catalyst composed of a composite oxide containing iridium: button at 70 ·· 30 (mole number ratio) is formed on the electrode substrate formed by thermal decomposition.

554078

The lead concentration in the electrolyte started to rise from 4ppm to 12ppm. At the temperature of 50 ° C electrolytic bath, electrolysis was started at an anode current density of 40A / dm2 ^. When the electro-precipitated copper was wound into a foil shape, the same was used as in Example 1, and the lead concentration in the electrolytic solution was analyzed. In addition, the anode can be continuously operated without exchanging anodes in 10 months. Comparison You are the same as Example 1 except that lead dioxide is used instead of the lead carbonate of Example 1 for analysis. The results are shown in Table 1. · ', Comparison ^ Except that lead sulfate was used instead of lead carbonate in Example 1, the rest were the same as in Example 丨 and analyzed. The results are shown in Table 1 ° Comparison with yours * 3 The analysis is performed in the same manner as in Example 1 except that the lead carbonate of Example i is used instead of the lead carbonate of Example i. The results are shown in Table J. Comparative Example 4 For each liter of electrolyte, 0.2 g of metal lead powder having an average particle diameter of 45 / zm was added. When the lead concentration started to rise from 4 ppm and reached the leaf egg, it was the same as in Example 2 and electrolysis was started. ; The electrodeposited copper was wound into a knot shape, and at the same time, the error concentration in the electrolytic solution was analyzed in the same manner as in Example 1. The analysis results are shown in Table 1. ° / After 6 months of operation, a thickness of 554078 is produced in the width direction of the copper foil. 5. Description of the invention (7) The degree of uneven distribution makes it impossible to wind the copper foil. In addition, when the anode was removed from the electrolytic cell and investigated, it was confirmed that the reason was that the electrode catalyst coating was partially consumed, and that the thickness of the copper foil was not changed due to the consumption of the electrode catalyst coating. Even.

C: \ 2D-C0DE \ 90-10 \ 90118853.ptd Page 10 554078 V. Description of the invention (8) [Table 1] Changes in lead concentration in dilute sulfuric acid Example 1 Example 2 Comparative example 1 Comparative example 2 Comparison Example 3 Comparative Example 4 Time Lead Carbonate Lead Carbonate Lead Dioxide Lead Sulfate Metal Lead Powder Metal Lead Powder 1 10.4 1.9 0.9 1.2 7.8 2 8.8 10.7 9.3 5.0 8.4 9.3 3 12.2 9.2 5.6 9.3 4 1 1 1.9 7.1 5.3 10.4 6 10.4 6.6 8.0 6.8 7.6 7 y 11.8 6.6 8.0 6.8 8 y 11.1 11.5 6.4 8.4 7.0 7.9 9 y 11.3 6.9 7.1 5.9 13 y 1 1.6 7.6 15 y 11.3 7.5 22 y 1 1.2 8.4 27 y 1 1.7 7.6 29 y 12.1 7.6 34 Said 11.8 7.2 41 Said 12.2 8.1 43 Said 12.1 8.6 Draw Circles Page 11 C: \ 2D-CQDE \ 90-10 \ 90118853.ptd 554078 5. Description of the invention (9) [Effects of the invention] The effect of the invention Carbonate allows the lead concentration in the electrolyte to be maintained at a high level of 10 ppm or more, and it is also possible to rapidly precipitate stable lead dioxide on the insoluble metal electrode as described above. The lead dioxide can exert the function as an electrode catalyst for oxygen generation, and significantly prolong the life of the anode. [Explanation of component number] 1 2 3 4 5 6 7 8 Copper foil manufacturing equipment Electrolytic cell Electrolytic bath Cathode cylinder Anode Gap for electrolyte supply Copper copper box

C: \ 2D-OODE \ 90-10 \ 90118853.ptd Page 12 554078 Brief Description of Drawings Figure 1 is a drawing explaining the manufacturing equipment of metal foil. Page 13 C: \ 2D-CODE \ 90-10 \ 90118853.ptd

Claims (1)

54078 ,, Announcement 6. Application Patent Scope 1. A method for manufacturing a metal foil, which is a method for manufacturing a metal foil from a sulfuric acid acid solution, characterized by the use of a platinum group metal or platinum group metal formed by using The anode is covered with an oxide, and lead carbonate is added to the sulfuric acid acid solution of the electrolytic solution, so that the electrolysis can be performed while the lead concentration in the electrolytic solution is maintained above 10 ppm. \\ 312 \ 2d-code \ 90-10 \ 90118853.ptd Page 14