JPH0270095A - Method and device for continuously electrolyzing metallic material - Google Patents

Abstract

PURPOSE:To impart a pattern corresponding to a penetrating-hole pattern on a metallic material by bringing the rolled electrode assembly consisting of the upper layer of a screen having the penetrating-hole pattern, an intermediate layer contg. a paste, and the lower layer of a rolled electrode into contact with the material surface. CONSTITUTION:A material 6 impregnated with an electrolyte paste and a screen 5 made of a material inert to the paste and having a penetrating-hole pattern are concentrically arranged on a rolled electrode 7 to form a rolled electrode assembly 20. Meanwhile, a metallic material 2 is continuously delivered from a delivery means 1, supported by a guide roll 3, and conveyed. The assembly 20 is closely attached to the material on a holder 8, and a current is applied to the material 2 and the electrode 7 to cause electrolysis. As a result, a pattern corresponding to the penetrating-hole pattern of the screen 5 can be clearly imparted to the surface of the material 2, and the material 2 is wound on a winding means 9.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method and apparatus for electrolytic treatment of metal materials, which can be used for fine electrolytic processing, etching, plating, coloring treatment, etc. of metals.

<Conventional technology> Conventionally, methods for performing fine electrolytic treatment on metal materials include:
There is a photoresist method (for example, Japanese Patent Publication No. 15705/1983) in which a portion of a metal material other than the portion to be processed is coated with a resist.

In the above photoresist method, (1) creation of an original image, (2)
Creation of original plate by photolithography, (3) Pretreatment of surface to be processed, (4) Application of photosensitive liquid, -(5) N light, (6) Development, (7)
) Resist coating on surfaces other than the processed surface of the workpiece, (8) Electrolytic treatment, (9) Cleaning, (1o) Resist removal, (11)
There is a problem in that it requires very complicated processes such as cleaning, drying, and finishing, which inevitably leads to high costs.

<Problems to be Solved by the Invention> The present invention solves the above-mentioned drawbacks of the prior art, and enables processing such as etching, plating, and coloring to be carried out in fine processing using simple means and without using an electrolyte. It is an object of the present invention to provide a method and apparatus for electrolytic treatment of metal materials, which can provide extremely clear results even when the treatment is performed.

Means for Solving the Problems> The inventors of the present invention have conducted extensive research in order to eliminate the drawbacks of the conventional technology such as the complexity described above, and have discovered a pattern that is intended to be applied to a paste electrolyte and a metal material. By using a screen, it is possible to electrolytically treat any patterned area without using any resist, by making sure that the current concentrates on the patterned area that needs to be electrolytically treated. Electrolytic treatment is performed immediately by pre-treating the surface, and then the same level of processing as conventional technology can be performed by simply cleaning, drying, and finishing the material, making it possible to perform high-speed processing even for microfabrication at low cost. We have discovered that this is the case, and have arrived at the present invention.

That is, the present invention has a screen that is made of a substance that does not react with electrolyte paste (hereinafter simply referred to as paste) and has a perforated pattern to be electrolytically treated as the top layer, and has an intermediate layer that holds the paste below. , using an electrode assembly configured in a roll shape, further having a roll-shaped electrode therebelow, and leaching the paste held in the intermediate layer to the outside of the electrode assembly through the screen; By rotating the electrode assembly closely and synchronously with the surface of the moving metal material to be treated, and conducting electrolytic treatment by passing electricity between the rolled electrode and the metal material through the screen and paste,
Provided is a continuous electrolytic treatment method for a metal material, characterized in that an electrolytic treatment pattern corresponding to the through-hole pattern of the screen is applied to the surface of the metal material.

Further, there is a continuous electrolytic treatment method for a metal material in which the metal material is a cut plate or a strip.

Further, it is preferable that there be a continuous electrolytic treatment method for metal materials, in which the electrolytic treatment of the metal materials is electrolytic etching, electrolytic plating, or electrolytic coloring.

Preferably, the metal material is a band-shaped body, and the band-shaped body and the electrode assembly are brought into close contact over a partial arc of the circumferential surface of the electrode assembly.

In addition, the present invention has a screen made of a substance that does not react with the electrolyte paste and has a perforated pattern to be electrolytically treated as the top layer, an intermediate layer that holds the paste below, and further below that a screen in the form of a roll. An electrode assembly having an electrode and having a roll-like structure as a whole; means for supporting and transporting a metal material in close contact with the electrode assembly; and a paste and a screen between the rolled electrode and the metal body. Provided is a continuous electrolytic treatment apparatus for metal materials, characterized in that it has means for supplying current through the apparatus.

The intermediate layer is preferably made of a substance that does not react with the paste and can impregnate and permeate the paste.

Further, it is preferable to include means for supplying the paste to an intermediate layer of the electrode assembly.

Further, it is preferable that the rolled electrode is a hollow body and has a plurality of discharge ports on its circumferential surface through which the paste supplied into the hollow body is discharged from the paste supply means.

Further, it is preferable to have means for discharging the paste after the electrolytic treatment.

The electrolytic treatment apparatus for metal materials of the present invention will be explained in detail below.

In the present invention, the metal material to be electrolytically treated refers to a material having at least a surface portion of a metal portion that can be electrolytically treated. Examples include not only various steel plates and non-ferrous metal plates, but also laminated materials of these metal thin plates or foils with ceramics, plastics, wood, etc., or materials whose surfaces are coated with these metal materials by any means. .

Further, the paste-like electrolysis X (hereinafter simply referred to as paste) used differs depending on the intended treatment.

As the plating paste, solutions containing plating species such as ordinary plating solutions and mixed solutions of various metal salts and acids or alkalis are used, such as sodium polyacrylate,
Any method can be used as long as it is made into a paste by adding organic thickeners such as sodium alginate and xanthan gum and/or inorganic thickeners such as zeolite, water glass, colloidal silica, colloidal alumina, and sodium silicofluoride. Even manufactured ones can be used.

Coloring pastes include alkalis such as sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, butic acid, chromic acid, dichromic acid, phosphoric acid, formic acid,
Using an aqueous coloring solution containing acids such as acetic acid, malonic acid, maleic acid, malic acid, tartaric acid, or salts of the above alkalis or acids alone or in combination, organic thickeners such as sodium polyacrylate, sodium alginate, xanthan gum, etc. are used. Any paste produced by adding an agent and/or an inorganic thickener such as zeolite, water glass, colloidal silica, colloidal alumina, or sodium silicofluoride can be used. .

Etching and processing pastes include alkalis such as hydric soda, acids such as hydrochloric acid, sulfuric acid, nitric acid, chromic acid, dichromic acid, butic acid, and/or salts of the above alkalis or acids alone or in combination. Of course, it can be made into a paste as it is or by adding water, or it can be made into a paste by adding a pasting agent such as sodium polyacrylate, silicon dioxide, alumina, water glass, or sodium alginate. Even manufactured ones can be used.

It also has such tackiness and viscosity that it will not spread beyond the supplied width even if it is supplied onto a metal material. Therefore, even minute processing can be performed precisely.

In the present invention, the electrolytic treatment can include etching, plating, coloring treatment, etc. depending on the paste used and the electrolytic conditions.

First, a first configuration example and operation of the electrolytic treatment apparatus of the present invention will be explained based on FIG. 1.

The metal material 2 is continuously fed out from the feeding means 1, is conveyed while being supported by the guide rolls 3, and is wound up by the winding means 9. The desired electrolytic treatment described above is performed using the roll-shaped electrode assembly 20 at the electrolytic treatment position where the support stand 8 is installed in the middle.

In the present invention, the electrode assembly 20 has an electrolytic treatment screen 5 having a perforated pattern on the uppermost layer, an intermediate layer 6 made of an electrolytic paste-impregnated material impregnated with paste, and further below it. An electrode having a rolled electrode 7 is used.

The screen for electrolytic treatment used in the present invention may be a screen made of nylon, tetron, polyester, etc. with a resist printed on it, which is used for ordinary screen printing as long as it does not react with the solvent for electrolytic treatment. It may be a stamped sheet of fluororesin, stainless steel, high Ni alloy, etc., and only the patterned portion for electrolytic treatment is provided with through holes through which the electrolytic treatment solvent can pass. Also,
At least the surface layer of this screen must be composed of an electrically insulating layer.

The paste-impregnated material constituting the intermediate layer may be any material as long as it can be impregnated with the paste described above, such as woven fabrics such as polyester fibers and alumina fibers, non-woven fabrics, sponges, porous bodies made of ceramics or synthetic resins, etc. However, in any case, it is necessary to be able to impregnate and penetrate the paste.

Note that the intermediate layer 6 does not necessarily have to be composed of such an impregnated material, and it can be used as long as the screen does not deform (for example, when the rigidity of the soufflen is high or when the width of the metal plate to be treated is narrow). Alternatively, the gap may simply be formed between the screen and the rolled electrode.

Further, under the paste-impregnated material 6, there is a rolled electrode 7 whose at least the surface is made of a corrosion-resistant metal or alloy such as stainless steel, titanium, nickel, platinum, or a conductive material such as carbon or conductive resin.

Then, the paste-impregnated material 6 impregnated with the paste and the screen 10 are arranged concentrically around the roll-shaped electrode 7, and the screen 10 is formed into a roll shape as a whole, and the electrode assembly 20 is assembled.
Nasu.

The paste is permeated and leached from the intermediate layer 6 through the screen 10, brought into close contact with the metal material 2 on the electrolytically treated material support 8, and subjected to etching, engraving, coloring, etc. according to the selected paste and electrolytic conditions. Electrolytic treatment is performed.

In addition, as means for supplying electricity during the electrolytic treatment, the metal material 2 is supplied with a conductor roll 4, and the rolled electrode 7 is supplied with a power supply line or a conductive brush (not shown) (see Fig. 3, 16).
Power is supplied from a suitable power source (not shown) by a power source such as a power source.

At this time, since the electrode assembly 20 with the screen 5 as the uppermost layer is disposed on the metal material 2, a pattern corresponding to the perforation pattern provided on the screen is applied to the surface of the metal material.
The metal material 2 is conveyed along guide rolls 3 and rotated in synchronization with the movement of the electrode assembly 20 to undergo continuous electrolytic treatment.

Since the working surface of this electrode assembly 20 is constantly rotating, the temperature rise is small, and the adverse effects of the temperature rise can be prevented.

To synchronize the rotation of the electrode assembly 20 with the running of the metal material, there are two methods: simply pressing the electrode assembly 20 against the moving metal material and passively rotating it by friction, and driving the electrode assembly 20 itself separately. There is a method of rotating the metal material by controlling it to a circumferential speed corresponding to the running speed of the metal material using a means, but the latter method is advantageous in terms of preventing slippage.

Next, FIG. 2 shows a second configuration example.

In FIG. 2, the paste residue on the screen 5 after the electrolytic treatment is removed by the paste discharge means 10 after electrolytic treatment is performed in the same manner as in the first configuration example. The paste discharge means 10 has a loop of endless belt-like cloth 10b, which is rotationally driven by a drive roll 10a.

In other words, the paste remains attached to the surface of the screen 5 even after the electrolytic treatment, but the paste after the electrolytic treatment is picked up by the rotating belt-shaped cloth 10b by this discharge means, and the belt-shaped cloth 10b with the paste residue attached is cleaned. Fs 1
It is washed at 0e, then dried at drying means 10f, and then recycled.

Then, from the screen 5 from which unnecessary paste has been removed, new paste is leached out from the paste-impregnated material, and the patterned screen 5 is brought into close contact with the metal material 2 again, and electrolytic treatment is performed.

By incorporating this discharge means 10, it is possible to remove once-used paste adhering to the screen surface and clean the screen, so even finer electrolytic treatment can be performed continuously and damage to the screen can be avoided. few.

Next, FIG. 3 shows a sectional view of an example of the configuration of an electrode assembly 20 provided with paste supply means in the electrolytic treatment apparatus of the present invention.

In the electrode assembly 20, the rolled electrode 7 is a hollow body, and one end of the hollow body is connected to a paste supply tube 15 by a pipe joint 14 with a rotary seal mechanism.
5, the paste is supplied from the outside. The supplied paste enters the intermediate layer 6 through the multiple discharge ports 18 of the hollow body, and roughly passes through the holes in the screen 5 and oozes out to the outside thereof. At this time, paste armpit leakage prevention stopper 17
It is recommended that the paste be installed to prevent the paste from leaking and contaminating other parts. Note that the other end of the hollow body is connected to a roll shaft 19 for transmitting driving force in order to rotate the electrode assembly 20.

Further, in order to adjust the supply amount of the base paste, the discharge port 18 for supplying the paste is preferably configured so that the paste is uniformly impregnated without local unevenness by using the opening supply method in two steps.

By using this paste supply means, a large amount of metal material can be processed continuously, which is efficient.

Further, by using the paste discharging means together with the paste discharging means, a large amount of metal material can be processed more efficiently, and the processing apparatus can be made more compact.

FIG. 4 shows an example of a structure in which the method of contact between the metal material and the electrode assembly is improved in the case where the metal material is a band-shaped body in the present invention.

When the metal material is a strip-shaped body, the electrode assembly 200 is placed along a part of the circumferential surface, a current is supplied by the conductor roll 4, and the metal material 2 is pressed, thereby omitting the support stand 8 for electrolytic treatment. In addition, the contact length between the metal material and the electrode assembly can be increased, and therefore the electrolytic treatment time can be increased.

Further, as described above, if the present apparatus is equipped with paste supply means/discharge means, the processing apparatus can be made more compact.

In addition, if necessary, it is possible to install optional metal cleaning and drying equipment before and after the electrolytic treatment section of this device, and perform pre-treatment and/or post-treatment of metal materials simultaneously with electrolytic treatment. do not have.

<Example> The present invention will be specifically explained below based on Examples.

(Example 1) Processing and etching 1.
Using a paste electrolyte made by adding 5% xanthan gum and using the apparatus shown in Figure 1, 0.5xlOOx20
A 00 mm 5US304 strip was electrolytically processed under the following conditions. The screen has a perforated pattern with crosses 1 mm wide and 4 x 4' mm arranged at 4 mm intervals vertically and horizontally, using a plate-making method using a nylon monofilament screen (200 mesh) photosensitive emulsion.

The above-mentioned screen had a cylindrical shape with a diameter of 204 mm and a height of 100 mm, and was set on an electrode having a diameter of 200 mm and a paste impregnated material having a thickness of 2 mm wound around the electrode.

Moving speed of 5US304 strip of treated material: 6cm/mi
The electrodes were treated with a distance of about 2 mm, an electrolytic current of 15 mA, an electrolytic voltage of about 2 V, a polarity of the material to be treated, and a paste supply rate of about 2 c c /min.

As a result, the above cross pattern (width approx. 1mm, 4x4mm,
depth of approximately 10 μm) to 0 without adding any processing strain.
．． The entire surface of a 5x100x2000mm plate could be etched in about 30 minutes.

(Example 2) Plating Using a paste electrolyte made by adding 3% sodium polyacrylate to a 5% H2So4 + 5% Cu SO4 aqueous solution, using the apparatus shown in Figure 2, 0.4xlOOx20
A cross-shaped plating similar to that in Example 1 was applied to a 00 mm rolled steel plate under the following conditions.

The screen material and shape are the same as in Example 1.

Movement speed of cold rolled steel as the material to be treated; i Q cm/min
, interpolar distance 1IIIt: approx. 2mm, electrolysis current: 10mA
, Electrolytic voltage: about 1.5 V, polarity: + for the electrode, - for the material to be treated, and the paste supply rate was about 4 cc/min.

In about 20 minutes, copper plating in a cross pattern was applied to the entire surface of a 0.4 x 100 x 200' Omm board.

With this device, the surface of the material to be treated can be plated into any shape by simply changing the patterned screen without using a resist agent.

(Example 3) Color development Using a paste electrolyte made by adding 35% sodium polyacrylate to a 10% H2So4 aqueous solution, Example 1 was applied onto a titanium strip measuring 05 x 10100 x 2000 using the apparatus shown in Figure 3. A cross-shaped color development process similar to that in .2 was performed under the following conditions.

The screen material and pattern are the same as in Example 1.2.

Moving speed of titanium strip of treated material = 60cm/mi
n, distance between electrodes: approximately 2 mm, constant voltage control at electrolytic voltage = 15 V, polarity: electrode -, material to be treated +, paste supply amount.
It was processed at about 200 cc/min.

A gold-colored criss-cross pattern could be obtained on the entire surface of the titanium plate without using a resist agent.

<Effects of the Invention> According to the method of the present invention, a taraki (viscous) paste is used without using an electrolyte, the paste and electrolytic conditions are appropriately selected, and the electrode and the material to be treated are moved relative to each other. By doing so, a variety of processes such as fine processing, etching, coloring, and plating can be performed continuously.

[Brief explanation of the drawing]

1 and 2 are diagrammatic side views showing various configuration examples of the electrolytic treatment apparatus for metal materials of the present invention. FIG. 3 is a sectional view showing an example of the configuration of an electrode assembly including paste supply means. FIG. 4 is a diagrammatic side view showing an example of a configuration in which the method of contacting the metal material and the electrode assembly is improved when the metal material of the present invention is made into a band-shaped body. Explanation of the symbols 1... Feeding means for band-shaped metal material, 2... Band-shaped metal material, 3... Guide roll 4... Conductor roll for current supply, 5... Screen for electrolytic treatment, 6. . . . Intermediate layer, 7. Roll-shaped electrode, 8. Support for electrolytic treatment, 9. Band-shaped metal material winding means, 10. Electrolytic paste discharge means, 10a. Paste discharge. strip cloth drive roll, 10b
... Band-shaped cloth, 10e... Band-shaped cloth washing tank, 10f... Band-shaped cloth drying means, 11... Paste agent, 12... Roll reinforcing material, 13... Roll bearing, 14... Pipe break with rotary seal mechanism 15...Paste supply tube, 16...Conductive brush, 17...Paste armpit leakage prevention horn <-18...
・Paste discharge port, 19... Roll shaft for driving force transmission, 20... Electrode assembly

Claims (9)

[Claims] (1) A screen made of a substance that does not react with the electrolyte paste (hereinafter simply referred to as paste) and having a perforated pattern to be electrolytically treated is the top layer, an intermediate layer holding the paste is provided below the screen, and using an electrode assembly having a roll-like configuration as a whole with a rolled electrode underneath, the paste retained in the intermediate layer being leached to the outside of the electrode assembly through the screen; By rotating the assembly closely and synchronously with the moving surface of the metal material to be treated, and conducting electrolytic treatment by passing electricity between the rolled electrode and the metal material through the screen and paste,
A method for continuous electrolytic treatment of metal materials, characterized in that an electrolytic treatment pattern corresponding to the perforation pattern of the screen is applied to the surface of the metal material. (2) The method for continuous electrolytic treatment of metal materials according to claim 1, wherein the metal material is a cut plate or a band-shaped body. (3) The continuous electrolytic treatment method for metal materials according to claim 1 or 2, wherein the electrolytic treatment of the metal materials is electrolytic etching, electrolytic plating, or electrolytic coloring. (4) The continuity of the metal material according to any one of claims 1 to 3, wherein the metal material is a band-shaped body, and the band-shaped body and the electrode assembly are brought into close contact over a partial arc of the circumferential surface of the electrode assembly. Electrolytic treatment method. (5) A screen made of a substance that does not react with the electrolyte paste and having a perforated pattern to be electrolytically treated is the top layer, an intermediate layer that holds the paste is formed below the screen, and a rolled electrode is further below that. an electrode assembly configured in a roll shape as a whole; means for supporting and conveying a metal material in close contact with the electrode assembly; and a paste and a screen between the rolled electrode and the metal body. 1. An apparatus for continuous electrolytic treatment of metal materials, characterized in that it has means for supplying electricity. (6) The continuous electrolytic treatment apparatus for metal materials according to claim 5, wherein the intermediate layer is made of a substance that does not react with the paste and can impregnate and permeate the paste. (7) The continuous electrolytic treatment apparatus for metal materials according to claim 5 or 6, further comprising means for supplying the paste to an intermediate layer of the electrode assembly. (8) The rolled electrode is a hollow body, and has a plurality of discharge ports on its circumferential surface through which the paste supplied into the hollow body is discharged from the paste supply means. The continuous electrolytic treatment apparatus for metal materials according to any one of the above. (9) The continuous electrolytic treatment apparatus for metal materials according to any one of claims 5 to 8, further comprising means for discharging the paste after the electrolytic treatment.