WO1999067448A1

WO1999067448A1 - Freely detachable insoluble anode

Info

Publication number: WO1999067448A1
Application number: PCT/JP1998/003307
Authority: WO
Inventors: Ryuichi Otogawa; Shinji Yamauchi; Koichi Soda; Hirokatsu Shimizu
Original assignee: Daiso Co., Ltd.
Priority date: 1998-06-22
Filing date: 1998-07-24
Publication date: 1999-12-29
Also published as: EP1026288A4; EP1026288A1

Abstract

A freely detachable anode (7) for continuously applying electroplating to a blank plating sheet such as a steel strip, capable of avoiding the occurrence of local non-conduction portions by a plurality of recess portions formed in the anode surface for inserting bolt heads, and avoiding non-uniform plating in the product, comprising an anode plate (1) freely detachably fitted to an electrode substrate (2) by a plurality of bolts (3) screwed from the anode plate side, wherein the sum of the occupied area of each of a plurality of recess portions (9) formed in the anode surface (8) for inserting the bolt heads inside an imaginary region of one rectangle defined by the length of the anode plate and an arbitrary width of the full width is not greater than 10 %, preferably not greater than 8 % and most preferably not greater than 5 %, of the area of the imaginary region.

Description

Description Insoluble anode that can be easily observed

The present invention relates to an insoluble anode for electrolytic plating, which is a main component of an electrolytic plating apparatus for continuously applying electrolytic zinc plating, electroplating, and the like to a plating base plate. The present invention relates to an insoluble anode detachably attached to an electrode substrate.

Background art

Conventionally, in order to continuously apply electrolytic zinc plating, electrolytic tin plating, etc. to a metal plate such as a steel strip, it is necessary to use an insoluble anode as an insoluble anode on the side of the electrode base opposite to the metal plate for electrode reaction and conductivity. In this case, a lead or lead-based alloy is used. However, this anode had problems such as contamination of the plating bath due to lead eluted from the build-up portion and deterioration of the plating film quality. As an alternative to this, various insoluble anodes having an electrode active coating layer containing, as an electrode active material, an electrode active material on an anode material have been proposed.

Generally, in this type of anode, the electrode active layer deposited on the anode material is extremely thin compared to the anode coated with lead or a lead-based alloy, and therefore, such as an electro-zinc plating line, etc. When a steel strip runs near the anode at high speed, the steel strip may come into contact with the anode due to flapping of the steel strip, causing local damage to the electrode active layer on the anode surface and losing the anode activity. Such local deactivation causes unevenness in the product and lowers the quality of the product, which necessitates repair and replacement of the anode. Japanese Utility Model Laid-Open No. 2-133659 discloses that the anode plate is divided into a plurality of pieces to facilitate repair of the anode, and the divided pieces of the anode plate are electrically conductively bolted to the electrode substrate from the electrolytic surface side. There has been proposed a split-type insoluble anode for an electro-mechanical, which is removably attached to the electrode. Japanese Utility Model Laid-Open Publication No. 63-131,764 discloses that a second electrode substrate coated with an electrode active material is attached to and detached from the first electrode substrate from the electrode active layer side by using a titanium bolt. A composite electrode for electrolysis that has been mounted as possible has been proposed.

As described above, these publications indicate that the anode plate is removably attached to the electrode base from the anode plate side by a bolt, but the mounting position of the bolt is not disclosed at all. Absent.

As described in the above publication, in an electrode in which the anode plate is attached to the electrode substrate by a bolt from the electrolytic surface side, that is, the electrode active shoulder side, the time required for replacing the anode plate is greatly reduced. The bolt mounting hole is generally not covered with the electrode active layer, and therefore no current flows. Even if the bolt mounting hole is covered with the electrode active layer, the mounting tool may damage the electrode active layer, and the special shape of the part requires a great deal of labor to cover the electrode active layer. Is economically disadvantageous. In addition, the electrode active layer covering the bolt mounting holes is peeled off from the electrode active layer in a short time due to scratches and the like, and the portion cannot be energized. Even if the head of the port is covered with the electrode active layer, as in the case of the bolt mounting hole, the electrode cannot be electrically connected due to damage or short life of the electrode active layer. If such a conductive part is present locally, it causes appearance problems such as unevenness of the product. SUMMARY OF THE INVENTION An object of the present invention is to provide, in an insoluble anode of an electroplating apparatus for continuously electroplating a plating plate such as a belt, a plurality of recesses formed on the anode surface for bolt head fitting. Accordingly, an insoluble anode capable of avoiding the occurrence of a local non-conductive portion is provided, thereby preventing the occurrence of unevenness or the like in a product. Disclosure of the invention

The insoluble anode according to the present invention is an insoluble anode in which the anode plate (1) is detachably attached to the electrode substrate (2) by several ports (3) screwed from the anode plate side. In the anode (7), a plurality of recesses (9) formed in the anode surface (8) for bolt head fitting are formed by one of the length of the anode plate and an arbitrary width in the entire width. The sum of the areas occupied by the recesses (9) in the rectangular virtual area (hereinafter referred to as “arbitrary virtual area”) is 10% or less, preferably 8% or less, with respect to the area of the arbitrary virtual area. It is characterized in that it is preferably arranged to be less than 5%.

That is, the area of one arbitrary virtual area (Z1) (Z2) of a rectangle formed by the length (L) of the anode plate and one arbitrary width (W1) (W2) in the entire width The percentage of the sum of the recess areas is at most 10%, preferably at most 8%, most preferably at most 5%.

The area occupied by a plurality of recesses in an arbitrary virtual region means the entire area of the recess when one entire recess is in the arbitrary virtual region, and only a part of one recess is optional. When it is within the virtual area, it means the partial area within the same area.

Throughout this specification, the length direction is the 鑭 band indicated by the arrow (D). The width direction refers to the direction perpendicular to the direction of the arrow (D). The area of the concave portion (9) refers to the type of the concave portion (9) on the same surface as the anode surface (8). The anode plate (1) may be divided into a plurality of divided pieces.

It is preferable that two or more concave portions (9) adjacent in the longitudinal direction are arranged so that they do not lie on any one straight line in the longitudinal direction. That is, if one of the two concave portions (9) in contact with each other in the longitudinal direction is located on any one straight line in the longitudinal direction, the other is always deviated from the same straight line. It is preferable that the concave portion (9) is arranged.

As the anode plate (1), a plate obtained by depositing an electrode active layer containing a platinum group metal or an oxide thereof on an anode material is preferable.

INDUSTRIAL APPLICABILITY The insoluble anode according to the present invention is suitable as a main component of a continuous electrolytic plating apparatus for applying electrolytic zinc plating, electrolytic tin plating, and the like to a plating original plate such as a mesh band. . The insoluble anode according to the present invention will be specifically described with reference to the drawings. FIG. 1 is a plan view showing an example of an insoluble anode according to the present invention, and FIG. 2 is a vertical cross-sectional view showing an example of disposing the insoluble anode according to the present invention in a plating tank. 1 and 2, the anode plate (1) is detachably attached to the electrode base (2) by a plurality of bolts (3) screwed into the electrode base (2) from the anode plate side. The insoluble anode (7) is constituted. The insoluble anode (7) is placed with the anode plate (1) facing upward in the plating bath (6) stored in the plating tank (5), and the plating is above the insoluble anode (7). A steel strip (4) as a base plate is run in the direction of (D) along the insoluble graphite (7) at a required interval in a metal bath (6). Steel strip (4) is the cathode. Usually, another insoluble anode is also placed above the mesh band. The upper and lower anodes are plated on both sides of the Kaburagi belt, but the illustration of the upper insoluble anode is omitted for simplicity. Fig. 2 shows a horizontal type with the insoluble anode (7) arranged horizontally. Although the present invention is directed to a tacking device, the present invention is also applicable to a vertical jack device in which an insoluble anode is vertically arranged.

In FIG. 1, on the anode surface (8) of the insoluble anode (7), that is, on the surface facing the steel plate, a recess (9) for fitting the head of the bolt (3) for attaching the anode plate (1) to the electrode base (2). ) Are formed. In the left rectangular arbitrary virtual area (Z1) formed by the length (L) of the anode plate (1) and the arbitrary left width (Ϊ1) of the anode surface (8), a concave portion (9) is formed. ) Does not exist at all. Therefore, the ratio of the sum of the area occupied by the concave portions to the area of the arbitrary virtual region (Z1) is 0%. The right virtual rectangular arbitrary area (Z2) formed by the length (L) of the anode plate (1) and the right arbitrary width (W2) of the anode surface (8) includes a plurality of Each of the recesses (9) is entirely or partially present (see the hatched portion in FIG. 1). The total area occupied by these recesses (9) is about 7% or less of the area of the arbitrary virtual region (Z2). In the insoluble anode (7) shown in Fig. 1, the anode plate (1) consists of a single metal plate whose size matches the electrode substrate (2), while the anode plate (1) is shown in Figs. As shown, it may be divided into a plurality of pieces, for example, four pieces (10). Each of the divided pieces (10) is spread over one electrode base (2), and is detachably attached to the base (2) by a plurality of bolts screwed in from the anode plate side. ing.

In addition, a plurality of bosses are provided on each of the opposing surfaces of the anode plate (1) and the electrode substrate (2). A gap is formed between (1) and the electrode substrate (2), and the bolt is screwed into the butted boss from the anode plate side, so that the electrode plate (1) is connected to the electrode substrate (2). The butt surface of each boss is coated with platinum or the like, and the anode plate (1) is

It is preferable to secure the electrical contact in (2).

The running direction of the steel strip is indicated by an arrow (D) in FIGS. In the example shown in FIGS. 3 and 4, in the anode plate (1) composed of four divided pieces (10), the sum of the areas occupied by the plurality of concave portions (9) in the arbitrary virtual region is equal to the arbitrary virtual region. 10% or less of the area of the region.

Fig. 4 shows that in each of the divided pieces (10) of the anode plate (1), two recesses (9) adjacent in the longitudinal direction are both located on any one straight line in the longitudinal direction. An example in which the information is hidden so as not to exist. This arrangement is effective in preventing the spots on the mesh from continuously occurring in the running direction of the steel strip. FIG. 5 shows an example of an insoluble anode not belonging to the present invention. In FIG. 5, the anode plate (1) is similarly divided into four divided pieces (10), and each divided piece (10) is spread over one electrode substrate, and a plurality of pieces are placed on the same substrate. In the anode plate (1) consisting of four divided pieces (10), the total area occupied by several recesses (9) in an arbitrary virtual area is It exceeds 10% of the area of the area. The electrode substrate (2) according to the present invention is generally made of titanium metal, but may be a core material such as 鐧 having an outer surface lined with a corrosion-resistant material such as titanium. The anode material used for the anode plate (1) may be metallic titanium, titanium-tantalum, or titanium-tantalum. Titanium-based alloys such as luniobium and titanium-palladium are preferred. The shape of the anode material is generally plate-like. An anode material such as a mesh or a perforated plate may be attached to a metal plate. The meteorological pole material is, for example, a material obtained by subjecting a titanium plate to a grit-plast treatment using aluminum grit.

The main constituent of the electrode active layer to be deposited on the anode material is selected from platinum group metals or their oxides, particularly iridium oxide or iridium and titanium, tantalum, A mixed oxide with a valve metal such as niobium, tungsten or zirconium is preferred. Representative examples include iridium-tantalum mixed oxides, iridium-titanium mixed oxides, and the like. A mixed oxide composed of 10 to 97% by weight of metal in terms of metal and 90 to 3% by weight of valp gold is excellent in durability. Since the insoluble anode according to the present invention is configured as described above, the following effects can be obtained.

a) Since the sum of the areas occupied by the concave portions (9) in the arbitrary virtual region is less than 10% of the area of the arbitrary virtual region, it is possible to avoid the occurrence of a local non-conductive portion due to the concave portion. This makes it possible to prevent the occurrence of unevenness in the product.

b) By arranging the two concavities (9) adjacent in the longitudinal direction so that they do not lie on any one straight line in the longitudinal direction, unevenness in products can be prevented. The occurrence can be effectively prevented by one calendar year.

c) Since the anode plate (1) is detachably attached to the electrode base (2) from the anode plate side by a plurality of bolts (3), the work of replacing the anode plate can be performed easily. d) By constructing the anode plate attached to the electrode base with a plurality of divided pieces (10), the workability of repairing and replacing the anode plate can be further improved. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a plan view showing an example of an insoluble anode according to the present invention. FIG. 2 is a vertical cross-sectional view showing an example of disposing an insoluble anode according to the invention in a plating tank.

FIG. 3 is a plan view showing an example in which the anode plate is divided into a plurality of divided pieces.

FIG. 4 is a plan view showing another example in which the anode plate is divided into a plurality of divided pieces.

Figure 5 is the best mode for carrying out the plan view der Ru _Q invention showing an example of an insoluble anode which does not belong to the present invention

Hereinafter, examples of the insoluble anode according to the present invention will be described, but the present invention is not limited to these examples.

Example 1

As shown in FIG. 3, the anode plate (1) of this embodiment is composed of four split pieces (10). Anode material is a material of the split pieces (10), using an aluminum Nagri tree bets on a commercial titanium down plate (thickness 1 5 mm), was subjected to grid Topurasu preparative process empty pressure 4 K gf Z cm ³ Things. A solution having the following composition was applied to the anode material.

T a C 1 5 40 0 ra g

H ₂ I r C ls .6 H ₂ 0 1 3 0 0 mg

3 5% H C 1 1 ml

n-C 4 H 9 OH 10 ml It was dried for 10 minutes at 1 2 0 and then fired at 5 0 0 ^e electric furnace kept at C 2 0 minutes. This operation was repeated five times to form an electrode active eyebrow having an electrode active material amount of 10 g / m ^{2 in} terms of metal iris on the surface of the anode material. In this way, a plurality of divided pieces (10) of the anode plate in which the electrode material was coated with the electrode active layer containing the solid oxide were obtained.

The four divided pieces (10) were spread over one electrode substrate and attached to the substrate with a plurality of bolts to form an insoluble anode. In this example, in the anode plate (1) composed of four divided pieces (10), the sum of the areas occupied by the plurality of recesses (9) for bolt head insertion in an arbitrary virtual region is as follows. It was up to 5% of the area of the optional β-region. Example 2

Anode plate (1) consists of four split piece prepared in the same manner as in Example 1 (10) (Kimu厲I re Jiumu translated at the electrode active material weight 1 0 g Z m ^2), the divided A piece (10) was spread over one electrode substrate as shown in Fig. 4 and attached to the same substrate with a plurality of bolts to form an insoluble anode. In the anode plate (1) consisting of (10), two concavities (9) adjacent in the length direction are arranged so that they do not lie on any one straight line in the length direction. .

Also, in the anode plate (1) composed of four divided pieces (10), the sum of the areas occupied by the plurality of recesses (9) for bolt head insertion in the desired area is an arbitrary virtual value. Up to 8% of the area of the region. Comparative Example 1 As shown in FIG. 5, four divided pieces (10) (electrode active material amount of 10 g / m ^{2 in} terms of metal iridium) prepared in the same manner as in Example 1 were combined with one electrode. An insoluble anode was constructed by laying on the substrate and attaching it to the substrate with a plurality of bolts. In this example, in the anode plate (1) consisting of four divided pieces (10), the sum of the areas occupied by the plurality of recesses (9) in the arbitrary virtual region is the maximum with respect to the area of the arbitrary virtual region. Was 15%. Evaluation test

As shown in FIG. 2, each of the insoluble anodes produced in the examples and the comparative examples was installed in a plating apparatus, and in this plating apparatus, continuous zinc plating of the cord was performed by the following method. An ordinary A1 quilted steel strip was used as the plating plate. Further, by dissolving _{Z n S 0 4 · 7 H} 2 0 so that the澳度3 0 0 βΖ 1, respectively so that the H ₂ S 0 ₄ in concentration 5 0 gZ l Ion exchange water, A Zn plating bath was prepared. The plating bath was placed in a plating bath, heated to 60, degreased and then pickled, and the plating original plate was immersed in the plating bath. After that, adjusting the traveling speed of the main luck original sheet so that the relative flow rates of the main luck original plate and main luck bath is 2 Iotaitazeta seconds, main Tsu key current density l OO AZD m ² Niteme Tsu key attachment bulk 2 0 such that g Roh m ² performs electroplated luck, to obtain a zinc main Tsu key steel. The resulting zinc plating plate was examined for appearance and appearance. The appearance of the plating was visually evaluated on a three-point scale. The results are shown in Table 1.

0 Unevenness of recess area of product in arbitrary virtual area

Maximum value of summation percentage

Example 1 5% ◎

Example 2 8% 〇

Comparative Example 1 1 5% X

◎ No irregularities

〇 The unevenness is almost inconspicuous

X Applicability in industry with noticeable unevenness

The present invention relates to an insoluble anode for an electrolytic plating, which is a main component of an electrolytic plating apparatus for continuously applying an electrolytic zinc plating, an electrolytic tin plating or the like to a plating original plate.

Claims

The scope of the claims

1. At the anode surface (7), the anode plate (1) is detachably attached to the electrode base (2) by a plurality of bolts (3) screwed from the anode plate side. A plurality of recesses (9) for bolt head fitting formed in (8) are formed by one length of the anode plate and an arbitrary width in the entire width. A removable insoluble anode characterized in that it is arranged so that the total area occupied by the recesses (9) is 10% or less of the area of the virtual region.

2. The plurality of recesses (9) are arranged so that the sum of the areas occupied by the recesses (9) in the virtual region is 8% or less of the area of the virtual region. The insoluble anode according to claim 1, wherein the anode is an insoluble anode.

3. The plurality of recesses (9) are arranged such that the total area occupied by each recess (9) in the virtual region is 5% or less of the area of the virtual region. The insoluble anode according to claim 1, wherein

4. The insoluble anode according to any one of claims 1 to 3, wherein the anode plate (1) is divided into a plurality of divided pieces (10).

Two

5. The special feature is that two or more recesses (9) in contact with each other in the longitudinal direction are arranged so as not to be located on any one straight line in the longitudinal direction. 5. The insoluble anode according to any one of 1 to 4.

6. The method according to any one of claims 1 to 5, wherein the anode plate (1) is formed by coating an anode material with an electrode active material containing a platinum group metal or an oxide thereof. Insoluble anode.

7. The insoluble anode according to any one of claims 1 to 6, wherein the insoluble anode (7) is an anode of a continuous electroplating device.

Three