JPH0270093A - Method and device for electrolyzing metallic material - Google Patents

Abstract

PURPOSE:To render a minute pattern on the surface of a metallic material by applying an electrolyte paste on the metallic material surface through a screen having a penetrating-hole pattern and laminated on the surface of the metallic material, and electrolyzing the material. CONSTITUTION:The laminated body of a band-shaped metallic material 3 and a screen 2 having a penetrating-hole pattern and made of a material inert to the electrolyte paste 5b is delivered by a delivery means 1, supported by a guide 4, and transferred. The paste 5b in a vat 5a is continuously supplied to the laminated body on the upstream side of the transfer direction through a rolls 5c-5e, and applied on the material 3 through the pattern of the screen 2. A power is supplied to the material 3 and an electrode 6 on a holder 9 to cause electrolysis, and a pattern corresponding to the pattern of the screen 2 is rendered to the surface of the material 3. The paste 5b after electrolysis is picked up by the rotating band-shaped cloth 10b, and scraped by a doctor 10d into a paste reservoir 10c. The patterned material 3 is wound on a winding means 11 along with the screen 2.

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 an original plate by photolithography, (3) Pretreatment of the surface to be processed, (4) Application of photosensitive liquid, (5) Exposure, (6) Development, (7)
) Resist coating on surfaces other than the processed surface of the workpiece, (8) Electrolytic treatment, (9) Cleaning, (10) 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 feathers that are extremely clear even when the blades are drawn.

Means for Solving the Problems> The inventors of the present invention have conducted extensive research in order to solve the above-mentioned disadvantages such as the complexity of the conventional technology, and have found that it appears that they are applying it to paste electrolysis and metal materials. By using a screen formed with perforations, we have added a device that allows the current to concentrate on the pattern area to be electrolytically treated, making it possible to electrolytically process any pattern area without using any resist. This allows the surface of the material to be treated to be electrolytically treated, which has only been subjected to simple pre-IA filling such as cleaning and drying, and then cleaning, drying, and finishing treatment of the material as necessary. The present invention was completed based on the discovery that high-speed processing is possible even in low-cost microfabrication because the same level of processing as in the prior art can be performed.

That is, the present invention forms a laminate by closely adhering to the surface of a metal material a screen made of a substance that does not react with an electrolyte paste (hereinafter simply referred to as paste) and having a perforated pattern to be electrolytically treated. A paste is applied to a predetermined electrolytic treatment position of the laminate through a screen, and a pattern is applied to the surface of the metal material by electrolytically treating the metal material through the paste and the screen at the electrolytic treatment position. The present invention provides a method for electrolytically treating metals.

Further, it is preferable that both the metal material and the screen have a band shape, and that the electrolytic treatment is performed while continuously feeding out a coil that has been wound in advance as a laminate of the metal material and the screen.

The metal material and the screen are both in the form of a belt, and during continuous feeding and winding from each winding coil, they are brought into close contact with each other to form a laminate, and this is conveyed synchronously. It is preferable to perform the electrolytic treatment at the same time.

Further, it is preferable that the four-layered structure is adhered to each other by magnetic adsorption or adhesive.

Further, the electrolytic treatment is suitably any one of electrolytic processing, electrolytic etching, electrolytic plating, or electrolytic coloring.

Further, the present invention provides a means for feeding and a winding means for a laminate of a metal material and a screen, and a screen side of the laminate faces the laminate between the feeding means and the winding means. between the electrode and the metal material of the laminate via the screen, on the upstream side of the electrode position in the transport direction of the laminate;
A metal material comprising: means for supplying paste; means for discharging the paste downstream of the electrode position in the transport direction of the laminate; and means for energizing the metal material of the electrode and the laminate. There are several electrolytic treatment equipments.

Further, a feeding means and a winding means for each of the metal material and the screen with through-holes, and maintaining the metal material and the screen in a laminated state by keeping the metal material and the screen in close contact over a predetermined distance between the feeding means and the winding means. means, an electrode facing the laminate from the screen side of the laminate, and between the electrode and the metal material of the laminate via the screen, on the upstream side of the electrode position in the transport direction of the laminate;
A metal characterized by comprising means for supplying a paste, means for discharging the paste downstream of the electrode position in the transport direction of the laminate, and means for energizing the metal material of the electrode and the laminate. There is an electrolytic treatment equipment for materials.

Further, the electrode is preferably a flat plate or a roll.

Furthermore, it is preferable to include a cleaning device for the laminate or metal material and/or screen.

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 electrolyte (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. .

For etching and processing pastes, 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 may be used 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. Those manufactured by can also 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 fine processing can be performed precisely.

The screen used in the present invention may be a resist printed on a screen made of nylon, tetron, polyester, etc., which are used for ordinary printing as long as it does not react with the electrolytic treatment solvent, or nylon, PVC, fluororesin, stainless steel, etc. , a sheet made of a high Ni alloy, etc., may be stamped, and only the plating pattern portion is provided with through holes through which the electrolytic treatment solvent can pass. Furthermore, at least the surface layer of this screen needs to be composed of a layer having electrical insulation properties.

In the present invention, the electrolytic treatment is performed depending on the paste used.
Etching, plating, coloring treatment, etc. can be performed.

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

The screen 2 and metal material 3, which have been made into a laminated body in advance, are continuously fed out from the feeding means 1, conveyed while being supported by guide rolls 4, and wound up by the winding means 11. The desired electrolytic treatment described above is carried out using the paste 5b at the electrolytic treatment position where the support stand 9 is installed midway.

The laminate of the material to be treated and the screen has a magnetic adsorption layer (in the resin film of the screen,
Either use a screen with a layer in which magnetic powder is dispersed to form a laminate using magnetic force, or use a screen with an adhesive layer, such as an adhesive urethane rubber layer, to create an adhesive layer. Either force is applied to form a laminate, or adhesives such as vinyl acetate resin, acrylic resin, natural or synthetic rubber are applied to the screen, and the material to be treated and the screen are laminated using the adhesive force or adhesive force. Either method may be used.

When selecting the method for forming the above-mentioned laminate, consider the reactivity with the electrolytic treatment paste agent and the removability of the screen after treatment, and select a method that does not easily react with the paste agent and is easy to peel off after treatment. It's good to do that. Note that the laminate forming means is not limited to the above two methods.

Above the support base 9, in the illustrated example, a flat electrode 6 is arranged so that it can be appropriately positioned with respect to the stacked body by a holding means 7.

Between the electrode 6 and the metal material 3 of the laminate, at a position upstream of the electrode 6 in the radial direction of the laminate, a paste 5b for electrolytic treatment is passed from a paste supply vat 5a to a pick-up roll 5c, an intermediate roll 5d, and a coater. It is continuously supplied via the roll 5d. The paste is a laminate screen 2
It reaches the metal material 3 through the perforation pattern provided in the electrode 6.
The space between the laminate and the treated portion of the metal material 3 of the laminate is filled with the paste 5b.

In this way, while maintaining the state in which the paste is filled between the metal material 3 and the electrode 6 of the laminate, the metal material 3 is connected to the conductor roll 8, and the electrode 6 is connected to the electrode 6 through a power supply line (not shown). , is supplied with power from a suitable power source (not shown), and electrolytic treatments such as etching, plating, and coloring are performed depending on the selected paste and electrolytic conditions. At this time, since the screen 2 is placed on the metal material 3, a pattern corresponding to the pattern applied to the screen is applied to the surface of the metal material.

In addition, in the water equipment, if necessary, especially when long-term electrolytic treatment is required, the electrolytic treatment is performed for a certain period of time with the feeding of the laminate stopped, and once a certain area has been treated, An intermittent process of sending a fixed amount of the laminate may also be performed.

Since the paste that has been subjected to the electrolytic treatment described above is unnecessary, it is removed by the paste discharging means 1o at a position downstream from the electrode 6 in the transport direction of the laminate. The paste discharging means 1o has a loop of endless belt-like cloth 10b, which is rotationally driven by a drive roll 10a.

Downstream of the electrolytic treatment position, that is, downstream of the electrode 6, the paste is picked up by a rotating band-like cloth 10a, scraped off by a doctor 1°d, and stored in a paste reservoir 10c. After this, the band-like cloth 10b is washed +
li 10 e and then drying means 10
After drying at f, it is recycled.

The laminated body of the patterned metal material 3 and the screen 2, which has been electrolytically treated at the electrolytic treatment position and unnecessary paste has been removed, is wound up by a winding means.

In addition, if a long electrolytic treatment is required, a plurality of electrolytic treatment devices, support stands, electrodes, paste supply, and recovery means may be installed in one line. In this case, paste supply and recovery means may be installed only in the first stage and the last stage, if necessary.

FIG. 2 shows a second configuration example of the present invention.

The difference in configuration from the first configuration example shown in FIG. 1 is that the electrode 6 is not a flat plate but a roll type, and the paste discharge means 10 is a suction type rather than a loop of cloth. It is a point.

With flat electrodes, if electrolytic treatment is performed at high current density for a long time, the temperature of the electrode will rise, which may have an adverse effect on the electrolytic treatment, but with the roll-type electrode shown in this configuration example, the working surface is constantly rotating. Because of this, the temperature rise is small and its negative effects can be prevented.

Next, the third configuration example of the electrolytic treatment apparatus of the present invention will be explained.
This will be explained with reference to the figures.

The third configuration example is a modification of the first configuration example shown in FIG.
The difference is that the metal material 3 and the screen 2 are not a laminate from the beginning. Therefore, other explanations will be omitted.

That is, the metal material 3 is fed from the feeding means 1 to the winding means 11, whereas the screen 2 is fed separately from the feeding means 12 to the winding means 13. During feeding, both are formed into a laminate on the guide roll 4, and after electrolytic treatment, they are separated again and wound up.

Further, FIG. 4 shows a fourth configuration example of the electrolytic treatment apparatus of the present invention. The fourth configuration example is a modification of the second configuration example shown in FIG. 2, and the difference is that the metal material 3 and the screen 2 are not a laminate from the beginning. The explanation on this point is the same as that given for the third configuration example shown in FIG.

When using a rolled electrode assembly, the supporting stand 9 for electrolytic treatment as shown in the various configuration examples shown in FIGS. The electrolytic treatment can be performed by winding the laminate over a partial arc of the circumferential surface of the roll. This is shown in FIG. At this time, it is preferable to provide a presser roll 14 in order to hold down the laminate so that it is wound around the electrode 6.

With such a configuration, the electrolytic treatment time can be longer than in the examples shown in FIGS. 1 to 4.

The above-described apparatus of the present invention may be made of any material as long as it is suitable for electrolytic treatment, but it is preferable to use a highly corrosion-resistant material or a material coated with a corrosion-resistant coating for the members that come into direct contact with the electrolytic paste. For example, the tubes may be made of fluororesin, and the piston, cylinder, etc. may be made of 5US316 coated with fluororesin.

The same strip screen can be used in all examples, but in particular a screen with an adhesive layer on at least the final layer on the side in contact with the metal surface and/or a screen with a layer containing magnetic fine powder at least on the final layer is used. It is desirable to do so.

The electrolytic treatment electrode is an electrode for electrolytically treating a metal strip through a paste, and is preferably made of a substance that does not react with the electrolytic paste. For example, a Ti plate whose surface is plated with PT, a carbon plate, etc. are preferable. The same applies to the material of the rolled electrode, as long as the surface layer has high corrosion resistance and conductivity. Note that in order to maintain a constant distance from the material to be treated and to prevent short circuits, it is desirable to attach a substance that can be impregnated with paste and has excellent chemical resistance and insulation properties to the electrode surface.

As pre-treatment and post-treatment of the metal strip and screen, cleaning and drying means for the screen and metal strip can be provided after the feeding means and before the winding means of the apparatus. In particular, if cleaning and drying means are installed before the winding means, the paste discharging means can be omitted, and product quality is also improved.

Next, the electrolytic treatment method for metal materials according to the present invention will be described with reference to the electrolytic treatment apparatus shown in FIG. 1 as a representative example, but the present invention is not limited thereto.

The laminated body of the screen 2 and the metal material 3 fed from the feeding means 1 is subjected to electrolytic treatment at the electrolytic treatment position of the support base 9. The paste 5b is passed from the vat 5a to the roll 5 through the screen 2 between the electrode 6 and the metal material 3 of the laminate.
c.

It is supplied via 5d and 5e.

Electricity is supplied from an electrolysis power source (not shown) to the metal material 3 between the metal material 3 and the electrode 6 via a conductor roll 8,
The metal material 3 is electrolytically treated. At this time, since the screen 2 with a perforated pattern is interposed between the metal material 3 and the electrode 6, a pattern corresponding to the pattern is formed on the surface of the metal material 3 by electrolytic treatment. This pattern is realized by etching, plating, coloring, etc. depending on the selected paste and electrolytic conditions.

Since the paste after electrolytic treatment is unnecessary, it is removed from the laminate by the paste discharging means 10. The paste is removed by an endless belt-like cloth 10b rotated by a drive roll 10a, and the paste adhering to the cloth is scraped off by a doctor 10d and dropped into a paste reservoir 10c. After this, the band-shaped cloth 10b is washed by the washing device 10e, dried by the drying means 10f, and then circulated.

In this apparatus, stepwise electrolytic treatment may be performed as necessary.

When a roll electrode as shown in FIGS. 2 and 4 is used as an electrode, it is preferable to wrap the laminate around the circumferential surface of the roll electrode and perform the electrolytic treatment as shown in FIG. 5, as this allows for a longer electrolysis time.

In addition, it is not necessary to form the laminate from the beginning;
and may be formed later as shown in FIG.

The electrolytically treated metal material is wound up together with the screen in the configuration examples of FIGS. 1 and 2, and with the screen separated in the configuration examples of FIGS. 3 and 4.

In the configuration examples shown in FIGS. 1 and 2, the screen of the wound metal material is peeled off while being rewound separately, and the surface is subjected to finishing treatments such as cleaning and drying.

In the configuration examples shown in FIGS. 3 and 4, the surface of the metal material is subjected to finishing treatments such as cleaning and drying while being separately rewound before or after being wound up.

If it is undesirable for the electrolyte paste to remain on the surface of the metal material for a long time, it is preferable to perform the treatment according to the configuration example shown in FIG. 3 or 4 above.

<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, 0.5X100X20
00 mm of 5US304 was electrolytically processed under the following conditions.

Screen: Nylon monofilament screen (
A cross-shaped perforation pattern of 1 mm width and 4 x 4 mm was created vertically and 4 times horizontally using a plate-making method using photosensitive emulsion on a 200 mesh (200 meshes).
Arranged at mm intervals, laminate moving speed: 60 cm/min Electrodes: 5X1
Distance between 00x100mm flat plate electrodes: Approximately 2mm Electrolysis current: 2A Electrolysis voltage: Approximately 10V Polarity: Electrode 1 1 Material to be treated + Paste supply rate: Approximately 150cc/min.

As a result, the above cross pattern groove (width approximately 1 mm, 4 x 4 m)
m, depth of about 10 μm) could be processed on the entire surface of a 0.5 x 100 x 2000 mm plate in about 200 seconds without adding any processing strain.

(Example 2) Plating A paste electrolyte made by adding 3% sodium polyacrylate to a 5% H2So4 + 5% CuSO4 aqueous solution was used, and the apparatus shown in Figure 2 was used to produce a 0.4x100x2000
Plating in the same cross pattern as in Example 1 was applied to a cold-rolled steel sheet having a diameter of 1 mm under the following conditions.

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

Laminated body moving speed: 10 cm/min, distance between poles
Approximately 2 mm, Electrolysis current: 60mA, Electrolysis voltage: Approximately 7■, Polarity, electrode +, Paste supply amount of the treated material, Approximately 25 cc/min.

Patterned copper plating was applied to the entire board in about 20 minutes.

(Example 3) A paste-like electrolyte made by adding 3.5% sodium polyacrylate to a 10% H2SO4 aqueous solution was used, and using the apparatus shown in Fig. 3, it was applied on a titanium plate of 0.5 x 10100 x 2000. The same cross-shaped pattern coloring treatment as in Example 1.2 was performed under the following conditions.

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

Laminated body moving speed: 60 c m/min.

Distance between electrodes: approx. 2mm, Electrolytic voltage: Constant voltage control at 15V, Polarity: Electrode -, material to be treated is +, Paste supply amount: 150cc/+nin 0 Cross pattern colored in gold without using resist agent could be obtained over the entire surface of the titanium plate.

<Effects of the Invention> According to the method of the present invention, a thick (viscous) paste is used without using an electrolyte solution, the paste, electrolytic conditions, and an electric screen with a perforated pattern are appropriately selected, and the electrode By relatively moving the material and the material to be processed, a variety of processing such as fine processing, etching, coloring, and brushing can be performed.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are diagrammatic side views showing various configuration examples of the electrolytic treatment apparatus for metal materials of the present invention. FIG. 5 is a schematic side view showing another aspect of the electrolytic treatment of the roll electrode and the laminate. Explanation of symbols 1... Feeding means, 2... Screen with perforated pattern, 3... Band-shaped metal material, 4... Guide roll, 5... Paste supply means, 5a... For paste supply Bat, 5b... Electrolyte paste agent, 5c... Pick up roll, 5d... Intermediate roll, 5e... Application roll, 6... Electrode for electrolytic treatment, 7... Electrode holding means, 8. ... Conductor roll for current supply, 9... Support stand for electrolytic treatment, 10... Paste discharging means for electrolytic treatment, 10a... Band-like cloth drive roll for paste discharging, 10b
... band-shaped cloth, 10c... discharge paste reservoir, 10d... paste scraping doctor 10e...
Band-shaped cloth washing tank, 10f... Band-shaped cloth drying means, 11... Winding-up means, 12... Band-shaped screen feeding means, 13... Band-shaped screen winding means, 14... Presser roll.

Claims (9)

[Claims] (1) A laminate is formed by closely adhering a screen made of a substance that does not react with electrolyte paste (hereinafter simply referred to as paste) and having a perforated pattern to be electrolytically treated to the surface of the metal material, and A method for electrolyzing metals, characterized in that a paste is applied to a predetermined electrolytic treatment position of a laminate, and the metal material is electrolytically treated through the paste and a screen at the electrolytic treatment position, thereby imparting a pattern to the surface of the metal material. Processing method. (2) The method for electrolytic treatment of a metal material according to claim 1, wherein both the metal material and the screen have a band shape, and the electrolytic treatment is performed while continuously feeding out a coil that has been wound in advance as a laminate of the two. (3) The metal material and the screen are both in the form of a belt, and during continuous feeding and winding from each winding coil, they are brought into close contact to form a laminate, and this is conveyed synchronously. 2. The electrolytic treatment method for a metal material according to claim 1, wherein the electrolytic treatment is performed while the electrolytic treatment is performed. (4) The method for electrolytic treatment of metal materials according to any one of claims 1 to 3, wherein the laminate is adhered by magnetic adsorption or adhesive. (5) The electrolytic treatment method for metal materials according to any one of claims 1 to 4, wherein the electrolytic treatment is electrolytic processing, electrolytic etching, electrolytic plating, or electrolytic coloring. (6) a feeding means and a winding means for a laminate of a metal material and a perforated screen; an electrode facing the laminate from the screen side of the laminate between the feeding means and the winding means; and the screen. between the electrode and the metal material of the laminate, on the upstream side of the electrode position in the direction of transport of the laminate,
A metal material comprising: means for supplying a paste; means for discharging the paste on the downstream side of the electrode position in the transport direction of the laminate; and means for energizing the metal material of the electrode and the laminate. electrolytic treatment equipment. (7) A feeding means and a winding means for each of the metal material and the perforated screen, and maintaining the metal material and the screen in a laminated state in close contact over a predetermined distance between the feeding means and the winding means. means, an electrode facing the laminate from the screen side of the laminate, and between the electrode and the metal material of the laminate via the screen, on the upstream side of the electrode position in the transport direction of the laminate;
A metal characterized by comprising: means for supplying paste; means for discharging the paste downstream of the electrode position in the transport direction of the laminate; and means for energizing the metal material of the electrode and the laminate. Equipment for electrolytic treatment of materials. (8) The electrolytic treatment apparatus for metal materials according to claim 6 or 7, wherein the electrode is a flat plate or a roll. (9) The apparatus for electrolytic treatment of metal materials according to any one of claims 6 to 8, further comprising a cleaning device for the laminate, the metal materials, and/or a screen.