JP2005272875A - Electrolytic treatment method and device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method where in electrolytic treatment for a fastener chain, a ball chain or the like, the surface of the member to be treated can be uniformly and efficiently subjected to electrolytic treatment at a low cost, and to provide a device therefor. <P>SOLUTION: The member 10 to be treated is arranged in an electrolytic bath in such a manner that the electrolytic bath is divided, and also, the circulation of an electrolytic solution is substantially performed only between the components to be treated in the member to be treated and/or from the gaps therearound; a pair of electrodes 25a, 25b are separately arranged on both the sides of the member to be treated; and power is supplied to the electrodes, so as to perform electrolytic treatment. Preferably, the electrolytic treatment is continuously performed while moving the member to be treated. Alternatively, a plurality of members to be treated are stored in an electrically insulating storage tank for the members to be treated arranged so as to divide the electrolytic bath and through which the electrolytic solution can be circulated in such a manner that the circulation of the electrolytic solution is substantially performed only between the plurality of members to be treated and from the gaps therearound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a material to be treated, which is a continuous long member made of metal or an alloy or a plurality of members to be treated made of metal or an alloy connected as a constituent element, for example, a tooth or a stop member made of metal or an alloy ( Electrolytic treatment method and apparatus for a metal or alloy treated material such as a slide fastener chain including an upper stopper and a lower stopper, or a ball chain in which metal or alloy ball members are continuously connected as constituent elements About.

Common electrolytic treatment (anodization, electrolytic plating, etc.) is performed by immersing this object in the same electrolytic bath with the counter electrode as one of the electrodes to be surface-treated, and energizing them. It has been broken.
However, for example, a fastener chain of a slide fastener in which a large number of engagement teeth (elements) are fastened to one end edge in the longitudinal direction of the fastener tape at a predetermined interval, or a ball in which a large number of ball members are connected by a connecting member such as a string. In the case of an object to be processed that includes a plurality of metal members such as chains, the members (for example, adjacent teeth) are not electrically connected. It is difficult to process.

Therefore, as a method of performing the surface treatment on the constituent members of the material to be processed including such a plurality of metal members, for example, a fastener chain is wound around a non-conductive cylindrical holder, and each metal member is further wound. Wrap an electric conductor wire so as to contact the service tooth (see Patent Document 1), or wind a fastener chain around a conductive holder (see Patent Document 2), or make only the service tooth conductive. A method of performing a batch process in a state where the metal working teeth are electrically connected to each other is mounted on a holding rod (see Patent Document 3).
However, any of these methods is a method in which an electrode member (electrical conductor wire, conductive holder, conductive holding rod) is brought into direct contact with the tooth part and energized. There is a problem that the film tends to be non-uniform and spots are easily formed on a film formed by electrolytic treatment such as an anodized film. Moreover, since any method becomes a batch process, productivity is also bad.

Therefore, a method is also performed in which a fastener chain is prepared in a state where the engagement teeth are electrically connected in advance, and this fastener chain is continuously subjected to electrolytic treatment. For example, a fastener chain in a state where the engagement teeth are electrically connected to each other is produced by weaving a conductive thread into the engagement portion of the fastener tape (see Patent Document 4), and the fastener chain having the conductive thread is guided. It is continuously conveyed while being guided by a roller so as to pass through the electrolytic bath and continuously subjected to electrolytic treatment (see Patent Document 5).
In such a method, the entire dental dentition can be energized simultaneously and continuously subjected to electrolytic treatment, but the conductive yarn is expensive. There is a problem that metal is easily dissolved and productivity is poor.

As another method, there is known a method in which a plurality of minute parts such as a slide fastener engaging tooth, a stop member (upper stop and lower stop), and a ball of a ball chain are plated in advance by barrel plating or the like.
However, in the case of normal barrel plating, current easily flows in the electrolytic solution, and it becomes difficult to sufficiently flow in the vicinity of the material to be processed. In addition, when a fastener chain is prepared by performing electrolytic treatment on the service tooth in advance and then fastening to the fastener tape, a wire rod having a cross-sectional shape corresponding to the cross-sectional shape of the service tooth, which is a normal fastener chain manufacturing method (so-called Y bar) ), The process is long and cumbersome, and the manufacturing cost is expensive.

Japanese Patent Publication No. 36-257 (Claims) Japanese Patent Publication No. 36-11871 (Claims) Japanese Patent Publication No. 33-1459 (Claims) Japanese Patent No. 2514760 (Claims) JP 2003-193293 A (Claims)

  The present invention has been made in view of the above-described problems of the prior art, and a main object thereof is a slide fastener chain including, for example, a metal or alloy engagement tooth or a stopper member (upper stopper, lower stopper). In addition, in the electrolytic treatment of a ball chain or the like in which a metal or alloy ball member is continuously connected as a constituent element, the processing non-uniformity caused by direct contact of the electrode with the metal or alloy treated member is solved. In addition, a method and an apparatus therefor are provided that can perform treatment without electrically connecting the dental dentition using a conductive thread, and can efficiently perform electrolytic treatment uniformly and at low cost on the surface of the member to be treated. There is to do.

In order to achieve the above object, according to a first aspect of the present invention, there is provided an electrolytic treatment method, the first aspect of which comprises partitioning the electrolytic bath in the electrolytic bath and substantially covering the electrolytic bath. The material to be treated is arranged so that the electrolyte solution can be circulated only between the components to be treated of the treatment material and / or the gaps around the component, and a pair of electrodes are arranged on both sides of the material to be treated. In addition, the electrolytic treatment is performed by supplying power to the electrode.
This method can be suitably applied to continuous processing, and electrolytic treatment can be performed continuously while moving the material to be processed.

  The second aspect of the electrolytic treatment method of the present invention comprises a plurality of members to be treated in an electrically insulating material storage tank that is arranged so as to partition the electrolytic bath and in which an electrolytic solution can flow. A material to be treated including a plurality of materials to be treated is accommodated so that the electrolyte can be circulated substantially only between the materials to be treated and the gaps around the materials, and both sides of the material to be treated are stored. A pair of electrodes are arranged apart from each other, and the electrolytic treatment is performed by supplying power to the electrodes.

  In any of the above-described electrolytic treatment methods, as a power feeding method, a direct current or a positive / negative symmetric or positive / negative asymmetric waveform (AC, pulse waveform, saw waveform, etc.) obtained by alternately inverting voltage or current is used. be able to. A particularly preferable power supply method is a method in which a cycle in which a counter electrode to be applied is reversed and applied for one or more cycles after applying a positive or negative asymmetric waveform in which DC or voltage or current is alternately reversed to positive and negative for a certain time is repeated. is there.

  Any material can be used as the material to be treated as long as at least a part thereof is made of metal or alloy. However, the electrolytic treatment method of the present invention can be applied to a continuous long member made of metal or alloy or a plurality of materials made of metal or alloy. Material to be treated consisting of members that are continuously connected with the processing member as a constituent element, in particular, a slide fastener chain including a metal or alloy service tooth or a stopper member (upper stopper and / or lower stopper), or metal Alternatively, the present invention can be advantageously applied to a ball chain in which ball members made of an alloy are continuously connected as constituent elements.

In addition, the electrolytic treatment method of the present invention can be applied to any method for electrically modifying the surface of a material to be treated, such as anodization, electrolytic plating, electrolytic polishing, and electrolytic degreasing.
The conditions for the electrolytic treatment can be appropriately set according to the form, material, etc. of the material to be treated, but when the material to be treated includes a member to be treated made of aluminum or an aluminum alloy as a constituent element, and anodizing the material, It is preferable to perform anodic oxidation at an electrolytic voltage of 20 V or higher using a waveform that is alternately reversed between positive and negative with a direct current or a frequency of 10 kHz or less.
When the electrolytic treatment is electrolytic polishing, it is preferable to perform electrolytic polishing using a waveform in which positive and negative frequencies of 5 Hz to 200 Hz are alternately reversed in a bath containing potassium hydroxide and / or sodium hydroxide.

Furthermore, when the material to be treated includes a member to be treated made of copper-zinc alloy, stainless steel, or zinc as a component, and when performing electroplating on these, using a waveform in which DC or a frequency of 10 Hz or less is alternately inverted, Electrolytic plating is preferred.
Further, when the electrolytic treatment is electrolytic degreasing, it is preferable to perform electrolytic degreasing at a voltage of 5 V or less using a waveform in which positive and negative frequencies of 100 Hz to 1 kHz are alternately reversed in a potassium hydroxide and / or sodium hydroxide bath.

  Furthermore, according to the second aspect of the present invention, there is provided an electrolytic treatment apparatus capable of suitably performing the electrolytic treatment method, wherein the first aspect is to fractionate the electrolytic cell and the electrolytic cell. A partition wall having an opening for flowing the electrolyte solution and a material insertion portion formed in the wall so as to cross the opening, and spaced apart on both sides of the partition wall It has a pair of electrodes. In a preferred embodiment, a leak receiving tank is disposed below the electrolytic tank, and a circulation line for sending the electrolytic solution in the leak receiving tank to the electrolytic tank is provided between the electrolytic tank and the leak receiving tank. It has been.

  Further, the second aspect of the electrolytic treatment apparatus of the present invention is an electrolytic tank, an electrically insulating material storage tank that is disposed so as to fractionate the electrolytic tank and through which an electrolytic solution can flow, It has a pair of electrodes that are spaced apart on both sides of the material storage tank. In a preferred embodiment, the material storage tank is a cylindrical porous rotating barrel, and preferably a plurality of protrusions are formed on the inner peripheral surface of the porous rotating barrel.

  According to the first aspect of the electrolytic treatment method of the present invention, in the electrolytic bath, the electrolytic bath is partitioned, and substantially between the components to be treated of the material to be treated and / or the gap around the components. Since the material to be treated is arranged so that the electrolyte solution is distributed only from, a pair of electrodes are arranged apart from both sides of the material to be treated, and the electrode is fed to perform the electrolytic treatment. It becomes easy for an electric current to pass through the interface vicinity with the electrolyte solution of a to-be-processed material. Therefore, the electrolytic treatment is efficiently performed, the electrolytic treatment without processing unevenness can be performed, and the bath concentration can be made lower than the conventional electrolytic treatment. In addition, when performing anodizing and electrolytic plating of fastener chains and ball chains, efficient electrolytic treatment can be performed simply by increasing the number of treatment steps in the conventional process without using expensive materials such as conductive yarns. It is possible to provide a fastener chain and a ball chain which can form a film having excellent durability and corrosion resistance without color unevenness and which have various decorative properties. In addition, by performing the electrolytic treatment continuously while moving the material to be treated, the electrolytic treatment can be performed at a relatively low cost with high productivity.

  Further, according to the second aspect of the electrolytic treatment method of the present invention, the material to be treated is placed in an electrically insulating material storage tank that is arranged so as to partition the electrolytic bath and through which the electrolytic solution can flow. Since the electrolytic treatment is performed in the housed state, it is a batch process. However, a material to be treated which is composed of a plurality of members to be treated or includes a plurality of members to be treated is substantially spaced between the members to be treated and the surrounding gaps. Since the material to be treated is accommodated so that the electrolytic solution is circulated only from the inside, the current can easily pass through the vicinity of the interface between the material to be treated and the electrolytic solution. Therefore, the electrolytic treatment is efficiently performed, the electrolytic treatment without processing unevenness can be performed, and the bath concentration can be made lower than the conventional electrolytic treatment. In addition, when performing anodizing treatment or electrolytic plating on small metal or alloy treated members such as fastener teeth, ball chain ball members, snap buttons, scissors, etc., durability without color unevenness, corrosion resistance, etc. Excellent film can be formed.

  Furthermore, according to the first aspect of the electrolytic treatment apparatus of the present invention, a continuous long member made of metal or an alloy or a member formed by continuously connecting a plurality of processed members made of metal or alloy as constituent elements. The treatment material can be continuously subjected to electrolytic treatment with high productivity and relatively low cost. Further, a liquid leakage receiving tank is disposed below the electrolytic tank, and a circulation line for sending the electrolytic solution in the liquid leakage receiving tank to the electrolytic tank is provided between the electrolytic tank and the liquid leakage receiving tank. According to the aspect, the electrolytic solution can be used efficiently, and the burden of waste liquid treatment can be reduced.

  Furthermore, according to the second aspect of the electrolytic treatment apparatus of the present invention, although it is a batch treatment, the electrolytic treatment is efficiently performed, and the electrolytic treatment without processing unevenness can be performed. Moreover, in the suitable aspect in which the said to-be-processed material storage tank is a cylindrical porous rotation barrel, Preferably several protrusion is formed in the internal peripheral surface of this porous rotation barrel, in a to-be-processed material storage tank Since the material to be treated is provided with the object agitation means for efficiently agitating the material to be treated, the uniformity of the electrolytic treatment can be further improved.

  As described above, the electrolytic treatment method and apparatus according to the present invention performs electrolytic treatment by an in-bath power feeding method without bringing an electrode into contact with a member to be treated and without using a special material such as a conductive yarn. However, since the electrolytic solution is circulated only between the members to be processed and the gaps around the members, the current can easily pass through the vicinity of the interface of the member to be processed with the electrolytic solution. As a result, it is possible to perform electrolytic treatment without processing unevenness, and to lower the bath concentration than conventional electrolytic treatment.

  As a means for allowing the electrolytic solution to flow only between gaps between and around the members to be treated, the first aspect is to partition the electrolytic bath in the electrolytic bath and substantially cover the electrolytic bath. The material to be treated is arranged so that the electrolytic solution is circulated only between the components to be treated of the treatment material and / or the gap around the component. On the other hand, in the second aspect, a plurality of members to be processed or a plurality of members to be processed are arranged in an electrically insulating material storage tank in which an electrolytic solution can be circulated so as to partition the electrolytic bath. The material to be treated is accommodated so that the electrolytic solution can be circulated substantially only between the material to be treated and the gap around it.

Hereinafter, the present invention will be described in detail while describing preferred embodiments of the present invention shown in the accompanying drawings.
First, FIGS. 2 to 4 show a material to be processed comprising a continuous long member made of metal or alloy, or a member obtained by continuously connecting a plurality of processed members made of metal or alloy as components, For example, a slide fastener chain including a metal or alloy service tooth or a stopper member (upper stopper and / or lower stopper), a ball chain in which metal or alloy ball members are continuously connected as components, An example of an electrolytic treatment apparatus that can be advantageously applied to a wire rod having a cross-sectional shape corresponding to a cross-sectional shape of a tooth (so-called Y bar) or the like is shown. A schematic configuration of an example of a slide fastener as a representative example is shown in FIG.

  As shown in FIG. 1, the fastener chain 1 includes a fastener tape 2 having a core portion 3 formed on one end edge side, and caulking and fixing (fixing) to the core portion 3 of the fastener tape 2 at a predetermined interval. And the upper stopper 5 and the lower stopper 6 fixed by crimping to the core portion 2 of the fastener tape at the upper end and the lower end of the engagement tooth 4. The slide fastener includes a pair of these fastener chains 1 facing each other and a slider 7 which is arranged between the engagement teeth 4 and is slidable in the vertical direction for engaging and disengaging the element 3. It should be noted that there are various types of engagement teeth fixed to the core portion 3 of the fastener tape 2 other than those shown in the drawings, and it goes without saying that the present invention can be applied to any of them.

  FIG. 2 shows a schematic configuration of the electrolyzer main body. The electrolytic cell 21 of the electrolytic treatment apparatus 20 is divided into two by a partition wall 22. The partition wall 22 includes an opening 23 through which the electrolytic solution flows, and a material insertion portion 24 formed so as to penetrate the partition wall 22 in a substantially vertical direction so as to cross the opening 23. In the example shown in the figure, an example is shown in which one electrolytic cell is manufactured by joining the side walls of two cells. That is, an opening is previously drilled at a position where the side walls of these two tanks face each other so that the opening 23 is formed when the side walls are joined to each other. A groove is formed in the direction in advance, and when the side walls are joined together, the partition wall 22 is formed, and at the same time, the workpiece insertion portion 24 is formed between them. It is not restricted to such a manufacturing method, The partition wall 22 in which the to-be-processed material insertion part 24 was previously formed so that the opening part 23 and this should be crossed can be divided into two chambers in one electrolytic cell 21. You may arrange | position.

In addition, electrodes 25 a and 25 b are respectively disposed in the chambers on both sides of the partition wall 22, and these are connected to the power source 26. The size of the electrodes 25a and 25b is preferably equal to or larger than the size of the opening 23, and the position thereof is separated from the partition wall 22, and the opposing projection area covers the opening 23. Any position can be set.
Further, as shown in FIG. 3, a leak receiving tank 27 is disposed below the electrolytic tank 21, and a circulation line 28 is provided between the leak receiving tank 27 and the electrolytic tank 21. The electrolytic solution L in 27 is sent to the electrolytic cell 21 by a pump 29.

  In addition, the size (width and depth) of the material insertion portion 24 formed in the partition wall 22 is set to be slightly larger than the width and thickness of the material to be processed, and the size of the opening 23 is It is set as appropriate according to the size of the member to be processed. For example, when the material to be treated is the fastener chain 1 and the member to be treated is the service tooth 4, as shown in FIG. 4, the width of the opening 23 is both the service teeth when the pair of fastener chains 1 are engaged. The total width of 4 is set to be approximately the same or slightly larger. By setting such a size, substantially only the portion of the tooth 4 to be processed of the fastener chain 1 is immersed in the electrolytic solution, so that the electrolytic solution impregnated in the fastener tape 2 is taken out. And the deterioration of the fastener tape 2 is prevented. Further, during the electrolytic treatment, since the electrolytic solution flows substantially only from the periphery of the tooth 4 (member to be treated) and / or from the gap between the teeth 4, the current is the same as the electrolytic solution of the tooth. It becomes easy to pass near the interface. Therefore, the electrolytic treatment is efficiently performed, and the electrolytic treatment without processing unevenness can be performed.

During the electrolytic treatment, the electrolytic treatment is continuously performed while the fastener chain inserted into the workpiece insertion portion 24 is sequentially conveyed downward as indicated by arrows in FIGS. 3 and 4. At this time, the electrolytic solution L leaks from the lower end opening of the workpiece insertion portion 24, but is collected in the leak receiving tank 27 disposed below. The electrolytic solution L collected in the leakage receiving tank 27 is sent to the electrolytic tank 21 by the pump 29.
In addition, in the said embodiment, although the leak receiving tank 27 was arrange | positioned under the electrolytic cell 21, an inner tank (equivalent to an electrolytic cell) is arrange | positioned in an outer tank (equivalent to a leak receiving tank), and an inner tank (electrolytic tank) The fastener chain carried out from the lower end opening of the workpiece insertion part (1) can be conveyed while being guided upward from between the inner tank and the outer tank by a guide roll. In this case, since the inner tank and the outer tank communicate with each other through the lower end opening of the processing object insertion portion, the liquid level of the electrolytic solution is the same in the inner tank and the outer tank, and the pump 29 is unnecessary.

  The electrolytic treatment method of the present invention is based on the principle of power supply in the bath. Here, the case of anodization will be described as an example. For example, both electrodes 25a and 25b are fed from a DC power source, If the electrode 25a is an anode and the other electrode 25b is a cathode, the surface of the engagement tooth 4 on the electrode 25a side is negatively charged, the surface of the electrode 25b side is positively charged, the surface on the electrode 25b side is oxidized, and an anodic oxide film is formed. It is formed. Next, when the electrode 25a is the cathode and the other electrode 25b is the anode, the surface of the engagement tooth 4 on the electrode 25b side is negatively charged, the surface of the electrode 25a side is positively charged, and the surface of the electrode 25a side is oxidized. As a result, an anodized film is formed. In this way, an anodized film is formed on the entire surface of the tooth. This principle of power supply in the bath can be applied not only to the anodizing treatment but also to all methods for electrically modifying the surface of the material to be treated, such as electrolytic plating, electrolytic polishing, and electrolytic degreasing.

5 and 6 show an example of a ball chain to which the electrolytic treatment method of the present invention can be suitably applied. The ball chain 30 has a structure in which a number of hollow spherical balls 31 made of metal or alloy are connected by a connecting member 32. When such a ball chain 30 is subjected to electrolytic treatment by the above-described electrolytic treatment apparatus 20, several ball chains 30 are aligned and passed through the workpiece insertion portion 24 so as to substantially match the width of the opening 23, The electrolytic treatment is continuously performed while being conveyed. Also in this case, during the electrolytic treatment, the electrolytic solution is circulated substantially only from the periphery of the ball chain 30 (material to be treated) and / or from the gap between the balls 31, so that the current is electrolyzed by the ball chain 30. It becomes easy to pass near the interface with the liquid. Therefore, the electrolytic treatment is efficiently performed, and the electrolytic treatment without processing unevenness can be performed.
When electrolytic treatment is performed on a linear material such as a Y bar, the electrolyte solution circulates between the Y bar inserted into the workpiece insertion portion 24 and the opening 23 with respect to the size of the opening 23. The size may be such that such a gap is formed. Moreover, when electrolytically treating such a linear object to be processed, the electrolytic process can be more suitably performed by conveying the object to be processed while rotating it.

  FIGS. 7 and 8 show the electrolysis of components such as the engagement teeth 4 of the fastener chain 1 as described above, or the balls 31 of the ball chain 30, or a small metal or alloy-treated member such as a snap button or a hook. An example of the electrolytic treatment apparatus of the present invention suitable for treatment is shown. In the electrolytic treatment apparatus 20, the electrolytic cell 21 is divided into two chambers by a partition wall 22 having an opening 23, and the opening 23 has an electrically insulating cylindrical object covered with an electrolytic solution. The processing material storage tank 40 is rotatably arranged around the rotation shaft 41. The material storage tank 40 is a cylindrical porous rotary barrel, and the outer peripheral wall and both side walls thereof are mesh-like, so that an electrolytic solution can flow therethrough. The outer peripheral wall and both side walls may be formed of a perforated plate. Further, a plurality of protrusions (projections) 42 are formed on the inner peripheral surface of the material storage tank 40 over substantially the entire length thereof. Similarly to the above-described embodiment, a pair of electrodes 25 a and 25 b are disposed on both sides of the processing object storage tank 40 so as to be separated from each other, and these are connected to the power source 26.

  In the electrolytic treatment apparatus 20 having such a structure, the height of the material to be treated 10 as a whole in the material to be treated storage tank 40 rotated during the electrolytic treatment is substantially equal to the liquid level of the electrolytic solution L. It is preferable to adjust the liquid level of the electrolytic solution L. As a result, it is possible to allow the electrolytic solution to flow substantially only between the members to be processed and the gaps around the members to be processed, so that the current easily passes through the vicinity of the interface of the member to be processed with the electrolytic solution. As a result, the electrolytic treatment is efficiently performed, and the electrolytic treatment without processing unevenness can be performed. In addition, since the plurality of protrusions (projections) 42 are formed on the inner peripheral surface of the processing material storage tank 40, the processing members stored in the processing material storage tank 40 are efficiently stirred. Therefore, the uniformity of the electrolytic treatment can be further improved.

  In any of the above-described electrolytic treatment methods, as a power feeding method, a direct current or a positive / negative symmetric or positive / negative asymmetric waveform (AC, pulse waveform, saw waveform, etc.) obtained by alternately inverting voltage or current is used. be able to. A particularly preferable power supply method is a method in which a cycle in which a counter electrode to be applied is reversed and applied for one or more cycles after applying a positive or negative asymmetric waveform in which DC or voltage or current is alternately reversed to positive and negative for a certain time is repeated. is there. Some waveform examples are shown in FIGS.

9A is a direct current, (B) to (D) are positive and negative symmetrical waveforms, (B) is an alternating current, (C) is a pulse waveform, and (D) is a saw waveform, (E) shows a pulse asymmetric waveform.
On the other hand, FIG. 10 shows an alternating current asymmetric type waveform, in which a waveform (a) having a larger negative value than positive and a waveform (b) having a smaller negative value than positive are alternately repeated. Perform electrolytic treatment.
By repeating the energization cycle in which the positive and negative asymmetrical waveforms are applied for a certain period of time and then reversed and applied alternately, it is possible to sufficiently perform the electrolytic treatment up to the engaged portion of the engagement teeth. .

  Moreover, the electrolytic treatment method of the present invention is an electrolysis in an acidic aqueous solution containing one or more of mineral acids or organic acids such as sulfuric acid, chromic acid, phosphoric acid, oxalic acid, malonic acid, maleic acid, and sulfamic acid. Anodizing treatment to form an anodic oxide film, or an electrolytic treatment in an acidic bath containing sulfuric acid and phosphoric acid, a neutral bath containing boric acid to produce a colored oxide film, nickel, chromium Electrolytic plating (electrodeposition) in which electrolytic treatment is performed in an electrolytic solution containing metal ions or metal compound ions such as gold and silver, electrolytic polishing or electrolytic treatment in which electrolytic treatment is performed in an alkaline aqueous solution such as sodium hydroxide and potassium hydroxide The present invention can be applied to any method for electrically modifying the surface of a material to be treated, such as degreasing. Since these processing methods are well known, their explanation is omitted.

The conditions for the electrolytic treatment can be appropriately set according to the form, material, etc. of the material to be treated, but when the material to be treated includes a member to be treated made of aluminum or an aluminum alloy as a constituent element, and anodizing the material, It is preferable to perform anodization treatment at an electrolytic voltage of 20 V or more and 50 V or less using a waveform in which direct current or a frequency of 10 kHz or less (0 to 10 kHz) is alternately reversed.
When the electrolytic treatment is electrolytic polishing, it is preferable to perform electrolytic polishing using a waveform in which positive and negative frequencies of 5 Hz to 200 Hz are alternately reversed in a bath containing potassium hydroxide and / or sodium hydroxide.

Further, when the material to be treated includes a member to be treated made of copper-zinc alloy, stainless steel, or zinc as a constituent element, and these are subjected to electrolytic plating, direct current or frequency of 10 Hz or less (0 to 10 Hz) is alternately reversed. Electrolytic plating is preferably performed using the corrugated waveform.
When the electrolytic treatment is electrolytic degreasing, electrolytic degreasing is performed at a voltage of 5 V or lower and 0.5 V or higher using a waveform in which positive and negative frequencies of 100 Hz to 1 kHz are alternately reversed in a potassium hydroxide and / or sodium hydroxide bath. It is preferable.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, it cannot be overemphasized that this invention is not what is limited to the following Example.

Example 1
Using the electrolytic cell 21 as shown in FIG. 2, a fastener chain having a service tooth made of an aluminum alloy as a constituent element is connected to the material insertion portion 24 formed on the partition wall 22, and the side surface of the service tooth and The periphery was placed so as to be exposed to the electrolytic bath, and the electrolyte was not allowed to pass from other parts.
1% sulfuric acid was used as an electrolytic solution, a pair of counter electrodes were arranged on both sides of the fastener chain, and a constant voltage electrolysis with a frequency of 3 kHz and 15 V was performed using an AC / DC superimposed waveform obtained by adding 5% DC component to AC. The electrolytic waveform was reversed every 30 seconds, and continuous electrolytic treatment was performed for 20 minutes while moving the chain in the longitudinal direction. As a result, an anodized film having a thickness of 3 microns could be uniformly formed on the aluminum alloy working tooth.

Example 2
Using an electrolytic cell 21 as shown in FIG. 2, 10 ball chains made of aluminum alloy were put in the longitudinal direction in a material insertion portion 24 formed on the partition wall 22.
5% sulfuric acid was used as an electrolytic solution, a pair of counter electrodes were arranged on both sides of the ball chain, and AC electrolysis was performed at a frequency of 100 Hz and a constant voltage of 10V. The ball chain was moved downward in the longitudinal direction while rotating around the longitudinal axis, and subjected to continuous electrolytic treatment for 30 minutes. As a result, an anodized film having a thickness of 1 micron could be uniformly formed on the aluminum alloy ball chain.

Example 3
Using an electrolytic cell 21 as shown in FIG. 7, it is made of an acid resistant resin having a large number of pores so that the electrolytic solution can pass through the opening 23 of the partition wall 22 divided into two chambers without resistance. When the barrel rotates, the porous cylindrical rotating barrel is placed so that the electrolyte does not pass through anything other than through the barrel, and the aluminum alloy service teeth for the fastener chain are inserted to a height of about 1/4 of the barrel. The electrolytic cell was filled with the electrolytic solution to the same position as the height of the tooth.
The electrolytic solution was 1% sulfuric acid, AC electrolysis was performed at a constant voltage of 1 kHz and a frequency of 35 V while rotating the barrel, and electrolytic treatment was performed for 60 minutes. As a result, an anodized film having a thickness of 3 microns could be uniformly formed on the aluminum alloy working tooth.

It is a front view which shows schematic structure of an example of the slide fastener which is a representative example of the to-be-processed material to which the electrolytic treatment method of this invention is applied. It is a general | schematic fragmentary broken perspective view which shows one embodiment of the structure of the electrolytic vessel of the electrolytic treatment apparatus of this invention. It is a schematic sectional drawing which shows one embodiment of the electrolytic processing apparatus of this invention. It is a partial explanatory view showing the correspondence between the opening of the partition wall of the electrolytic cell shown in FIG. 2 and the material to be processed (fastener chain) inserted into the material insertion part. It is a fragmentary perspective view which shows schematic structure of an example of the ball chain which is a typical example of the to-be-processed material which applies the electrolytic treatment method of this invention. FIG. 6 is a partial cross-sectional front view of the ball chain shown in FIG. 5. It is a general | schematic partially broken perspective view which shows the other embodiment of the electrolytic processing apparatus of this invention. It is a schematic sectional drawing of the electrolytic treatment apparatus shown in FIG. It is explanatory drawing which shows the example of an electrolysis waveform used for the electrolytic treatment method of this invention. It is explanatory drawing which shows the other example of the electrolysis waveform used for the electrolytic treatment method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fastener chain 2 Fastener tape 3 Core part 4 Teeth 5 Upper stopper 6 Lower stopper 7 Slider 10 Material to be processed 20 Electrolytic processing device 21 Electrolytic tank 22 Partition wall 23 Opening 24 Material to be processed insertion part 25a, 25b Electrode 26 Power supply 27 Liquid leak receiving tank 28 Circulation line 30 Ball chain 31 Ball 32 Connecting member 40 Material storage tank 42 Projection (projection)

Claims (14)

In the electrolytic bath, the material to be treated (10) is provided so that the electrolytic bath is partitioned and the electrolytic solution is substantially circulated only between the components to be treated of the material to be treated and / or from the gaps around the components. ) Is disposed, a pair of electrodes (25a, 25b) are disposed on both sides of the material to be treated, and the electrolytic treatment is performed by supplying power to the electrodes. The electrolytic treatment method according to claim 1, wherein the electrolytic treatment is continuously performed while moving the material to be treated (10). A material to be treated which is composed of a plurality of members to be treated or includes a plurality of members to be treated in an electrically insulating material to be treated (40) which is arranged so as to partition the electrolytic bath and through which the electrolytic solution can flow. The material to be treated (10) is accommodated so that the electrolyte can be circulated substantially only between the material to be treated and the space around it, and a pair of electrodes are separated from both sides of the material-contained material tank. (25a, 25b) is disposed, and the electrode is subjected to electrolytic treatment by supplying power to the electrode. 4. The electrolytic treatment method according to claim 1, wherein the power supply method uses direct current, or a positive / negative symmetric or positive / negative asymmetric waveform obtained by alternately inverting the voltage or current. The power feeding method is characterized by repeating a cycle in which a counter electrode to be applied is reversed and applying a current for one cycle or two or more cycles after applying a positive or negative asymmetric waveform obtained by alternately inverting DC or voltage or current for a certain period of time. The electrolytic treatment method according to any one of claims 1 to 3. 6. The electrolytic treatment method according to claim 1, wherein at least a part of the material to be treated is made of a metal or an alloy. The electrolytic treatment method according to claim 1, wherein the material to be treated is a slide fastener chain including a metal or alloy service tooth. 6. The material according to claim 1, wherein the material to be treated comprises a continuous long member made of metal or alloy or a member obtained by continuously connecting a plurality of members to be treated made of metal or alloy as constituent elements. The electrolytic treatment method according to any one of the above. The material to be treated includes a member to be treated made of aluminum or an aluminum alloy as a component, and the electrolytic treatment is an anodic oxidation treatment performed at an electrolytic voltage of 20 V or more using a DC or alternating waveform with a frequency of 10 kHz or less. The electrolytic treatment method according to any one of claims 1 to 8. An electrolytic cell (21), an opening (23) for distributing the electrolytic cell, and an object to be processed formed in the wall so as to cross the opening. An electrolytic treatment apparatus comprising: a partition wall (22) having a portion (24); and a pair of electrodes (25a, 25b) disposed on both sides of the partition wall. Furthermore, it has a liquid leakage receiving tank (27) disposed below the electrolytic tank, and a circulation line (28) for sending the electrolytic solution in the liquid leakage receiving tank to the electrolytic tank includes an electrolytic tank, a liquid receiving tank, The electrolytic treatment apparatus according to claim 10, wherein the electrolytic treatment apparatus is provided between the two. An electrolytic cell (21), an electrically insulating material storage tank (40) that is disposed so as to separate the electrolytic cell and through which the electrolyte can flow, and both sides of the material storage tank An electrolytic treatment apparatus comprising a pair of electrodes (25a, 25b) arranged apart from each other. The electrolytic treatment apparatus according to claim 12, wherein the material storage tank (40) is a cylindrical porous rotating barrel. The electrolytic treatment apparatus according to claim 13, wherein a plurality of protrusions (42) are formed on an inner peripheral surface of the porous rotary barrel.

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