JP2005060781A - Method and apparatus for surface treatment of aluminum support - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for anodic oxidation surface treatment of an aluminum substrate whereby deposition of metallic copper can be reduced. <P>SOLUTION: The long aluminum substrate material 12 is conveyed by a conveying means 16 so that it is dipped in an electrolyte 24 pooled in an electrolytic cell 20, and an electric current is supplied by a power source 30 to an electrode member 28 placed in the electrolyte 24 to induce an electrolytic reaction between the electrode member 28 and the aluminum substrate material 12. Here, copper ion concentration in the electrolyte 24 is reduced by taking the electrolyte 24 out of the electrolytic cell 20 through an electrolyte circulating path, passing the electrolyte 24 through a copper ion-remover 100 to collect copper ions in the electrolyte 24 and returning to the electrolytic cell, the electrolyte 24 from which the copper ions are removed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a surface treatment method and apparatus for continuously anodizing a long aluminum support used as a support for a lithographic printing plate.

  In general, a photosensitive lithographic printing plate (hereinafter referred to as “PS plate”) is used for offset printing.

  In such a PS plate production line, for example, a long strip-shaped sheet material made of aluminum or the like is sequentially drawn, and surface treatments such as graining treatment, anodizing treatment, silicate treatment, and other chemical conversion treatments are singly or appropriately combined. Then, after a photosensitive solution is applied to form a photosensitive layer, a PS plate is manufactured by cutting into a desired size.

  For the anodizing process in the production line of the PS plate, a surface treatment apparatus 11 using a so-called submerged power supply system as illustrated in FIG. 3 is used.

  In the surface treatment apparatus 11 illustrated in FIG. 3, the belt-shaped aluminum support 12 (aluminum substrate material) is conveyed along a conveyance path constituted by a plurality of conveyance rollers 14 and a guide roller 16 as a pass roller. Anodization is performed by sequentially immersing the feeder tank 18 upstream in the transport direction and the electrolytic tank 20 downstream in the transport direction.

  An acidic or alkaline feeding liquid 22 is stored in the tank of the feeding tank 18, and an electrolytic solution 24 is stored in the tank of the electrolytic tank 20. The aluminum support 12 is immersed in the power supply liquid 22 in the power supply tank 18 and the electrolyte solution 24 in the electrolytic tank 20 by being guided by the guide roller 16 and transported on the transport path. Each of these guide rollers 16 is brought into pressure contact with the surface of the aluminum support 12 with a predetermined pressure contact force and is guided by rolling. The aluminum support 12 thus transported is transported while being pulled with a required tension so as not to sag in the longitudinal direction.

  A plate-like power supply electrode 26 is disposed in the power supply tank 18 so as to face the surface (upper surface) of the aluminum support 12 immersed in the power supply liquid 22. Further, in the electrolytic cell 20, a plate-shaped electrolytic electrode 28 that is elongated along the transport direction is disposed so as to face the surface of the aluminum support 12 immersed in the electrolytic solution 24. The power supply electrode 26 is connected to an anode of a DC power source 30 as a power supply means via a bus bar, a cable, and the like. The electrolytic electrode 28 is connected to the cathode of a direct current power source 30 as power supply means via a bus bar and a cable.

  In this surface treatment apparatus 11, a current from a DC power source 30 as a power supply means flows from the power supply electrode 26 connected to the anode to the aluminum support 12 through the power supply liquid 22, and the current further flows through the aluminum support 12. A circuit is formed that flows in the direction of the electrolytic cell 20 and flows from the aluminum support 12 to the electrolytic electrode 28 via the electrolytic solution 24 in the electrolytic cell 20.

  Thereby, in the electrolytic bath 20, an appropriate amount of an anodic oxide film is formed on the surface of the aluminum support 12 by electrolytic reaction, and scratch resistance and abrasion resistance of the lithographic printing plate using the aluminum support 12 as a support. Abrasion is improved.

  In the electrolytic bath 20 in such a surface treatment apparatus 11, aluminum is eluted from the aluminum support 12 as an aluminum ion into the electrolytic solution 24 by an electrolytic reaction, and copper contained as an impurity in the aluminum support 12 is electrolyzed. It elutes into the liquid 24 as copper ions.

  The copper ions are stably present in the electrolytic solution 24 at the time of the electrolytic reaction. However, when the electrolytic reaction in the electrolytic bath 20 is not performed, the copper ions in the electrolytic solution 24 are changed to the aluminum support due to the difference in ionization tendency. 12. Deposited as metal copper on the electrolytic electrode 28 made of aluminum or the roller surface of the guide roller 16.

  For example, when current supply to the electrodes 26 and 28 is stopped in order to prevent the aluminum support 12 stopped in the electrolytic bath 20 from fusing, a part of the metallic copper deposited from the electrolytic solution 24 is a roller surface of the guide roller 16. May stick to the top.

  When the processing of the aluminum support 12 is resumed in such a state, the metal copper deposited on the guide roller 16 is supported by the aluminum when the guide roller 16 with metal copper adhered to the surface of the aluminum support 12 is pressed. It may move and adhere to the surface of the body 12.

  In this way, a photopolymer type lithographic printing plate (referred to as “CT plate” in the present specification), which is a particularly sensitive lithographic printing plate, is used with the aluminum support 12 having metallic copper attached to the surface as a support. When manufactured, the photosensitive material (photopolymer) applied to the surface of the aluminum support 12 reacts with electrons emitted from the metallic copper and dark polymerizes.

  The photopolymer dark polymerized on the CT plate remains as a spot-like residual film even after the CT plate is exposed to the laser and developed, so that the quality of the image printed using the CT plate as the original plate is lowered.

  Note that the residual film produced on the CT plate is an EPMA (EPMA: Electro Probe Micro-Analysis), that is, an X-ray microanalyzer, which irradiates a sample with an electron beam and measures the characteristic X-rays emitted. As a result of analysis by a device for elemental analysis of the region, it was revealed that a residual film was formed on the CT plate due to metallic copper because copper was detected in the residual film.

  Therefore, in the conventional surface treatment apparatus for aluminum material, when the current supply to the electrodes 26 and 28 is stopped for a predetermined threshold time or more, the electrolytic solution 24 in the electrolytic cell 20 is discharged to the storage tank 40. Then, copper deposition is suppressed by cutting the contact between the aluminum support 12 and the guide roller 16 and the electrolytic solution by emptying the electrolytic cell 20 (see, for example, Patent Document 1).

  However, in this surface treatment apparatus 11, copper is deposited before the contact between the aluminum support 12, the guide roller 16, and the electrolyte and the electrolytic solution is broken. That is, in the electrolytic solution 24 in the electrolytic cell 20, copper contained as an impurity in the aluminum support 12 is eluted and accumulated as copper ions, and the copper ion concentration is always in a high state. After the electrolytic reaction is stopped by interrupting, the electrolytic solution 24 in the electrolytic cell 20 is discharged to the storage tank 40, the aluminum support 12 and the guide roller 16 and the like, and the electrolytic solution 24 having a high copper ion concentration In the time until the contact is cut off, copper is deposited on the surfaces of the aluminum support 12 and the guide roller 16.

  Further, for example, when the copper content of the aluminum support 12 is as high as 200 ppm or more, the copper concentration in the treatment liquid increases, so the current supply from the DC power source 30 to the electrodes 26 and 28 is interrupted and the electrolytic reaction is stopped. Since the deposition of copper starts in a short time after being made, it is difficult to prevent the copper from being deposited on the aluminum support 12 or the guide roller 16.

For this reason, in the conventional surface treatment apparatus 11 as described above, when a CT plate is manufactured using the anodized aluminum support 12 as a support, the surface of the aluminum support 12 before the photopolymer is applied. To the extent that the photopolymer is darkly polymerized due to the influence of the metallic copper adhering to the surface and a spot-like residual film is formed on the image forming surface of the CT plate, the metallic copper is formed on the surface of the aluminum support 12. It was difficult to prevent adhesion.
JP 2001-262394 A

  The present invention reduces the copper ion concentration of the electrolytic solution in the electrolytic cell for performing the anodic oxidation surface treatment, so that even when the electrolytic treatment for the aluminum support for performing the anodized surface treatment in this electrolytic cell is interrupted, the electrolytic solution It is an object of the present invention to newly provide a surface treatment method and apparatus for an aluminum support that reduces the deposition of metallic copper from the metal and reduces the adhesion of metallic copper to the aluminum support.

  In the surface treatment method for an aluminum support according to claim 1 of the present invention, a copper ion is recovered from an electrolyte in an electrolytic cell in which an anodization surface treatment is performed by energizing the aluminum support. It is characterized by reducing the copper ion concentration.

  If the copper ion concentration of the electrolytic solution stored in the electrolytic cell is reduced by using the above-described surface treatment method of the aluminum support, for example, the current supply from the power source is stopped and the electrolytic reaction is stopped to anodic oxidation. Even when the surface treatment is interrupted, the deposition of metallic copper from the electrolytic solution can be reduced, and the deposition of metallic copper on the surface of the aluminum support can be reduced.

  The surface treatment apparatus for an aluminum support according to claim 2 of the present invention conveys an electrolytic bath for storing an electrolytic solution and a long aluminum support while being immersed in the electrolytic solution stored in the electrolytic bath. Supply current to the electrode member in order to cause an electrolytic reaction between the conveying means, the electrode member disposed in the electrolytic solution in the electrolytic cell so as to face the aluminum support, and the electrode member and the aluminum support. Power supply means, and copper ion removing means for removing copper ions in the electrolyte solution, which is disposed in the middle of the electrolyte circulation path after extracting the electrolyte solution from the electrolytic cell and returning it to the electrolytic cell again. It is characterized by having.

  According to a third aspect of the present invention, there is provided the surface treatment apparatus for an aluminum support according to the second aspect, wherein the copper ion removing means stores the electrolytic solution and is immersed in a metal member having a higher ionization tendency than copper. It is an ion removing tank.

  According to a fourth aspect of the present invention, in the surface treatment apparatus for an aluminum support according to the third aspect, a discharge port for discharging precipitated copper is provided at the bottom of the copper ion removing tank. .

  According to a fifth aspect of the present invention, in the surface treatment apparatus for an aluminum support according to the second or third aspect, a power source cathode is connected to a metal member, and a power source is connected to an insoluble conductive member immersed in an electrolytic solution. It is characterized in that an anode is connected to pass a current.

  According to a sixth aspect of the present invention, in the surface treatment apparatus for an aluminum support according to the second aspect, the copper ion removing means is a filter formed of a metal member having a higher ionization tendency than copper.

  A seventh aspect of the present invention is the surface treatment apparatus for an aluminum support according to the second aspect, wherein the copper ion removing means is made of an ion exchange resin that adsorbs copper ions.

  By configuring as described above, while conveying the long aluminum support so as to be immersed in the electrolytic solution stored in the electrolytic cell, the electrode member and the aluminum support are supplied with current from the power source to the electrode member. The electrolytic solution is extracted from the electrolytic cell through the electrolytic solution circulation path and the copper ion is removed through the copper ion removing means. By returning the electrolytic solution from which ions have been recovered and removed to the electrolytic bath through the electrolytic solution circulation path, the concentration of copper ions in the electrolytic solution stored in the electrolytic bath can be reduced.

  Therefore, if the copper ion concentration of the electrolytic solution stored in the electrolytic cell is always reduced by using the copper ion removing means, for example, the current supply from the power source is stopped and the electrolytic reaction is stopped to stop the anodized surface. Even when the treatment is interrupted, the deposition of metallic copper from the electrolytic solution can be reduced, and the deposition of metallic copper on the surface of the aluminum support can be reduced.

  According to the surface treatment method and apparatus for an aluminum support of the present invention, it is possible to reduce the adhesion of metallic copper to the aluminum support during anodizing surface treatment. For this reason, when a CT plate is produced by an anodized surface-treated aluminum support so that metallic copper does not adhere, when the photopolymer is applied, the photopolymer darkly polymerizes due to the influence of the metallic copper and the CT plate. Generation of a spot-like residual film on the image forming surface can be reduced.

  Hereinafter, an aluminum support surface treatment apparatus according to an embodiment of the aluminum support surface treatment method and apparatus of the present invention will be described with reference to FIGS. 1 and 2. In FIGS. 1 and 2, the same members as those in the conventional example shown in FIG. 3 described above are denoted by the same reference numerals for convenience of explanation.

  FIG. 1 shows a schematic configuration of the entire surface treatment apparatus for an aluminum support according to the present embodiment. The anodic oxidation surface treatment apparatus main body 10 constitutes a part of a production line for producing a photopolymer lithographic printing plate (CT plate) having a particularly high photosensitivity among lithographic printing plates.

  The anodized surface treatment apparatus main body 10 is configured to continuously perform electrochemical surface treatment (anodization treatment) by a submerged power feeding method on a strip-shaped aluminum support 12 (aluminum substrate material). Yes.

  The anodic oxidation surface treatment apparatus main body 10 includes a power supply tank 18 and an electrolytic tank 20, and a copper ion remover (copper ion removal tank) 100 as a copper ion removing means.

  Since the anodizing surface treatment apparatus main body 10 is configured to perform an anodizing process by a submerged power feeding system by using a feeding tank 18 and an electrolytic tank 20, a long belt-like aluminum support 12 is provided with a feeding tank 18. In order to constitute a conveying means for successively and continuously conveying on the conveying path immersed in the electrolyte solution 24 of the electrolytic bath 20 after being immersed in the power supply liquid 22, a plurality of conveying rollers 14 and a guide roller as a plurality of pass rollers 16 are arranged at predetermined positions on the conveyance path.

  Each of the guide rollers 16 constituting the conveying means has a surface layer portion having protection against the aluminum support 12 and chemical stability against sulfuric acid. High chloroprene rubber is formed as a raw material.

  Further, the electrolytic solution 24 is stored in the electrolytic bath 20. The electrolytic solution 24 is an acidic solution having a sulfuric acid concentration of 5 to 30 wt%. The aluminum ion concentration in the electrolytic solution 24 is adjusted to a range of 0.1 to 10 wt%, and preferably adjusted to a range of 0.7 to 5 wt%.

  Further, the liquid storage tank 40 is disposed vertically below the electrolytic tank 20. The electrolytic solution 24 is stored in the liquid storage tank 40, and adjustment raw materials for the electrolytic solution 24 such as aluminum sulfate, concentrated sulfuric acid (for example, 98% sol sulfuric acid), water, and the like can be supplied from outside the tank. ing.

  A liquid storage tank 40 is connected to the electrolytic tank 20 through a return pipe 34, a return pipe 66, an overflow pipe 36 and a liquid supply pipe 38.

  The overflow pipe 36 is arranged so that one open end thereof is connected to the vicinity of the upper end of the side wall portion of the electrolytic cell 20 and the other open end is immersed in the electrolytic solution 24 of the liquid storage tank 40. To do.

  As a result, when the level of the electrolytic solution 24 in the electrolytic tank 20 rises from the opening end of the overflow pipe 36, the electrolytic solution 24 in the electrolytic tank 20 flows out into the liquid storage tank 40 through the overflow pipe 36, The water level of the electrolytic solution 24 in the tank 20 is maintained at a predetermined upper limit water level.

  The liquid supply pipe 38 has one open end connected to the vicinity of the lower end of the side wall of the liquid storage tank 40 and opened to the electrolyte 24 in the liquid storage tank 40. The other opening end of the liquid supply pipe 38 extends upward from the electrolytic cell 20 and opens at a position on the liquid surface of the electrolytic solution 24.

  A main pump 44 is arranged in the liquid supply pipe 38, and the electrolytic solution 24 in the liquid storage tank 40 is pumped up and supplied into the electrolytic tank 20 by the operation of the main pump 44. In addition, a heat exchanger 48 that is controlled to heat or cool the liquid supply pipe 38 at a downstream side of the main pump 44 by a controller having a liquid temperature sensor (not shown) so that the liquid temperature of the electrolytic solution 24 is adjusted to an appropriate temperature. Is arranged.

  A liquid storage tank 72 connected to the power supply tank 18 through a liquid supply pipe 70 in which an overflow pipe 68 and a main pump 69 are arranged is provided below the power supply tank 18, similarly to the electrolytic tank 20. . In the liquid storage tank 72, the feeding liquid 22 is stored. Further, the liquid storage tank 72 is configured such that the adjustment raw material for the feed liquid 22 can be charged from outside the tank.

  In this anodic oxidation surface treatment apparatus main body 10, the aluminum support 12 is conveyed by the guide roller 16 from the power supply tank 18 to the electrolytic tank 20, so that the power supply liquid 22 in the power supply tank 18 and the electrolysis in the electrolytic tank 20 are obtained. It is immersed in the liquid 24. Each of these guide rollers 16 is brought into pressure contact with the surface of the aluminum support 12 with a predetermined pressure contact force and is guided by rolling. The aluminum support 12 thus transported is transported while being pulled with a required tension so as not to sag in the longitudinal direction.

  A plate-like power supply electrode 26 is disposed in the power supply tank 18 so as to face the surface (upper surface) of the aluminum support 12 immersed in the power supply liquid 22. Further, in the electrolytic cell 20, a plate-like electrolytic electrode 28 that is elongated along the transport direction is disposed so as to face the surface of the aluminum support 12 immersed in the electrolytic solution 24. The power supply electrode 26 is connected to the anode of the DC power supply 30 via a bus bar and a cable. The electrolytic electrode 28 is connected to the cathode of the DC power supply 30 through a bus bar, a cable, and the like.

  In the anodized surface treatment apparatus main body 10, a current from the DC power source 30 flows from the power supply electrode 26 connected to the anode to the aluminum support 12 through the power supply liquid 22, and further, the current passes through the aluminum support 12. A circuit is formed which flows in the direction of the electrolytic cell 20 and flows from the aluminum support 12 to the electrolytic electrode 28 via the electrolytic solution 24 in the electrolytic cell 20.

  Thereby, in the electrolytic bath 20, an appropriate amount of an anodic oxide film is formed on the surface of the aluminum support 12 by electrolytic reaction, and scratch resistance and abrasion resistance of the lithographic printing plate using the aluminum support 12 as a support. Surface treatment to improve the properties can be performed.

  Moreover, in the electrolytic bath 20 in such an anodized surface treatment apparatus main body 10, aluminum is eluted from the aluminum support 12 as an aluminum ion into the electrolytic solution 24 by an electrolytic reaction, and is contained as an impurity in the aluminum support 12. Copper elutes into the electrolytic solution 24 as copper ions.

  As shown in FIG. 1, the anodizing surface treatment apparatus main body 10 stores liquid below the electrolytic cell 20 on the electrolytic solution circulation path after drawing the electrolytic solution 24 from the electrolytic cell 20 and returning it to the electrolytic cell 20 again. A copper ion remover 100 that deposits copper ions in the electrolytic solution 24 generated in the course of the anodizing process as metallic copper and deposits and removes them is disposed at a position above the tank 40.

  The copper ion remover 100 has a relatively small liquid storage tank 102. One lower opening end portion of the introduction pipe 114 is connected to the liquid storage tank 102 so as to open to a lower portion thereof, and the other upper opening end portion of the introduction pipe 114 is positioned immediately below the liquid level of the electrolytic tank 20. The electrolytic solution 24 stored in the electrolytic bath 20 is configured to be naturally introduced into the liquid storage bath 102 through the introduction pipe 114 by gravity.

  In addition, one upper opening end of the discharge pipe 116 is connected to the liquid storage tank 102 so as to open to a position immediately above the liquid level when a predetermined amount of the electrolyte solution 24 is stored therein. The other lower opening end is disposed so as to open to a position on the liquid level of the liquid storage tank 40, and the electrolytic solution 24 stored in the liquid storage tank 102 overflows and naturally flows through the discharge pipe 116 by gravity. It is configured to be discharged into the liquid storage tank 40.

  In this anodized surface treatment apparatus main body 10, the electrolytic solution circulation path for drawing the electrolytic solution 24 from the electrolytic bath 20 and returning it back into the electrolytic bath 20 draws the electrolytic solution 24 in the electrolytic bath 20 from the introduction pipe 114. After the liquid is supplied to the liquid storage tank 102 and temporarily stored in the liquid storage tank 102, the liquid is supplied to the liquid storage tank 40 through the discharge pipe 116 and temporarily stored in the liquid storage tank 40. The pump 44 is pumped up and circulated in the electrolytic cell 20 through the liquid supply pipe 38. Note that the electrolytic solution circulation path may be shortened so as to be directly fed from the liquid storage tank 102 to the electrolytic tank 20 by a pump or the like.

  The copper ion remover 100 has a metal piece member 104 (which is a single piece of metal) having a higher ionization tendency than copper so as to be immersed in the electrolytic solution 24 stored in the relatively small liquid storage tank 102. It may be composed of metal pieces, or may be composed of a large number of metal pieces, or may be configured in the form of a mesh-shaped filter, and may be arranged on the metal piece member 104 depending on the difference in ionization tendency with copper. The copper ions are precipitated as metallic copper.

  Examples of the metal having a higher ionization tendency than copper used as the metal piece member 104 include aluminum, lead, iron, and tin. Aluminum is particularly desirable. This is because aluminum ions are eluted from the aluminum support 12 and are present in the electrolytic solution 24 in a large amount, so that even if dissolved in the electrolytic solution 24, they do not become impurities.

  Further, in the copper ion remover 100, one metal piece member 104 immersed in the electrolytic solution 24 stored therein is a cathode made of a metal having a higher ionization tendency than copper, and the other metal piece member 106 is insoluble conductive. Copper is electrolytically deposited by connecting the anode of the DC power supply 108 to the metal piece member 104 and connecting the anode of the DC power supply 108 to the metal piece member 106 to allow current to flow. You may comprise.

  In addition, the liquid storage tank 102 of the copper ion remover 100 is formed in a mortar shape at the bottom of the liquid storage tank 102 in order to extract the copper deposited and precipitated from the electrolyte 24 stored therein to the outside of the liquid storage tank 102. A discharge pipe 110 having one end opened as a discharge port formed at the lowest position in the center is installed. The other end of the discharge pipe 110 is opened outside the liquid storage tank 102, and an opening / closing valve 112 is installed in the middle thereof.

  As a result, the discharge pipe 110 as the discharge port is deposited on the metal piece member 104 from the electrolytic solution 24 by opening the opening / closing valve 112, and the precipitated copper is along the mortar-shaped bottom surface of the liquid storage tank 102. When the liquid drops and gathers at the opening of the discharge pipe 110 at the lowest position in the center, it is configured so that it can be drawn out together with the electrolytic solution 24.

  Further, in this copper ion remover 100, the copper deposited and precipitated from the electrolytic solution 24 as metallic copper is periodically removed using the discharge pipe 110 so as to be stored in the electrolytic cell 20. The copper ion concentration in the electrolyte solution 24 can be reduced.

  In addition, in the copper ion remover 100, a filter for filtering the metallic copper deposited from the electrolytic solution 24 is disposed in the liquid storage tank 102 instead of providing the discharge pipe 110, and this filter is periodically replaced. Alternatively, the deposited copper may be removed by cleaning or cleaning.

  The aluminum support 12 subjected to the anodizing surface treatment in the anodizing surface treatment apparatus main body 10 configured as described above is made of aluminum or an alloy containing aluminum as a main component (aluminum alloy) as a raw material in a predetermined shape having a long band shape. Form.

  The aluminum and aluminum alloy used as the material of the aluminum support 12 include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like as alloy components and impurities. Examples of materials suitable for the material of the aluminum support 12 include those specified by JIS A1050, JIS A1100, JIS A3003, JIS A3103, and JIS A3005.

  In the production line for producing the photopolymer lithographic printing plate using the above-described anodized surface treatment apparatus main body 10 for the aluminum support, the aluminum support 12 is not shown on the downstream side in the transport direction of the aluminum support 12. A highly sensitive photosensitive material (photopolymer) coating device and drying device for the body 12 are installed. The coating apparatus is provided with a photopolymer supply unit, and a plurality of metal coating rollers 60 are arranged. The photosensitive material supplied from the supply unit by the coating roller 60 is supplied to the surface of the aluminum support 12. The whole is stretched and the thickness of the photosensitive material is made uniform. Thereafter, the aluminum support 12 is transported from the coating device to the drying device, heated by a metal heating roller disposed in the drying device, the photosensitive material is dried, and a photosensitive layer is formed on the aluminum support 12. It has come to be.

  Next, the operation and operation of the surface treatment apparatus for an aluminum support according to the present embodiment configured as described above will be described.

  In this anodized surface treatment apparatus main body 10, a part of the long aluminum support 12 is immersed in the feeding tank 18 while being transported along the transport path, and the other part is immersed in the electrolytic tank 20. Then, as described above, electric power is supplied from the DC power source 30 to perform the anodic oxidation surface treatment on the aluminum support 12 immersed in the electrolytic solution 24 in the electrolytic cell 20.

  By this anodic oxidation surface treatment in the electrolytic bath 20, the copper ions eluted in the electrolytic solution 24 flow into the liquid storage tank 102 of the copper ion remover 100 through the introduction pipe 114, and on the metal piece member 104. The metal copper is deposited and deposited, and is deposited on the bottom of the liquid storage tank 102. The metallic copper collected at the bottom of the liquid storage tank 102 is periodically collected by opening the open / close valve 112 of the discharge pipe 110 and flowing it out together with the electrolyte 24.

  The electrolytic solution 24 from which the copper ions have been removed in the liquid storage tank 102 is discharged into the liquid storage tank 40 through the discharge pipe 116. The electrolytic solution 24 in the liquid storage tank 40 is pumped up by the main pump 44 and circulated into the electrolytic tank 20 through the liquid supply pipe 38.

  Therefore, since the copper ion concentration of the electrolytic solution 24 stored in the electrolytic cell 20 is always reduced using the copper ion remover 100, for example, the current supply from the DC power source 30 is stopped to stop the electrolytic reaction, and the anode Even when the oxidized surface treatment is interrupted, the amount of metallic copper deposited from the electrolytic solution 24 can be suppressed.

  For this reason, when a CT plate is produced using the aluminum support 12 that has been anodized so that metallic copper does not adhere as described above as a support, the photopolymer is affected by the influence of metallic copper when the photopolymer is applied. Can be prevented from forming a spot-like residual film on the image forming surface of the CT plate due to dark polymerization.

  In addition, in the surface treatment apparatus for an aluminum support according to the present embodiment, if the amount of metallic copper deposited from the electrolyte solution 24 is sufficiently suppressed, the electrode 26 as in the conventional surface treatment apparatus described above. , 28, when the current supply to the battery is stopped for a predetermined threshold time or longer, the electrolytic solution 24 in the electrolytic cell 20 is discharged to the storage tank 40 to empty the electrolytic cell 20, thereby the aluminum support 12 or By cutting the contact between the guide roller 16 and the electrolyte and the electrolytic solution, it is not necessary to suppress copper deposition. In this case, when the current supply to the electrodes 26 and 28 is stopped, the electrolytic bath 20 can be waited in the state where the electrolytic solution 24 is filled, so that the anodic oxidation surface treatment can be resumed immediately.

  Therefore, in the surface treatment apparatus for an aluminum support according to the present embodiment, the electrolytic solution is contained in the electrolytic cell 20 that is empty when the anodic oxidation surface treatment of the aluminum support 12 is resumed as in the conventional surface treatment apparatus. Therefore, the time for stopping the production line for producing the CT plate using the anodized aluminum support 12 as a support is reduced, and the electrolytic solution 24 is placed in the empty electrolytic cell 20. Since the time required for the refilling operation can be shortened, the decrease in productivity due to the stoppage of the production line can be prevented accordingly.

  Next, another configuration example of the surface treatment apparatus for an aluminum support according to the present embodiment will be described with reference to FIG.

  In the anodized surface treatment apparatus main body 10 shown in FIG. 2, an ion exchanger 120 that adsorbs copper ions in the electrolytic solution 24 generated in the process of anodization, which is the copper ion remover 100, is provided in the electrolytic cell 20. The electrolytic solution is drawn out from the electrolytic cell 20 and then placed in the electrolytic solution circulation path to be returned to the electrolytic cell 20 again.

  The ion exchanger 120 is filled with an ion exchange resin that adsorbs copper ions inside a container, and one open end of an introduction pipe 122 is connected to the lower part of the container, and the other end of the introduction pipe 122 is connected. The opening end is connected and arranged at a position immediately below the liquid level of the electrolytic cell 20. A liquid feed pump 124 is installed in the middle of the introduction pipe 122.

  Further, one open end of the discharge pipe 126 is connected to the upper part of the container of the ion exchanger 120, and the other open end of the discharge pipe 126 is opened to a position on the liquid surface of the electrolytic cell 20. To do.

  In the ion exchanger 120 configured as described above, by driving the liquid feeding pump 124, the electrolytic solution 24 stored in the electrolytic cell 20 is pumped out and introduced into the ion exchanger 120 through the introduction pipe 122. After the copper ions contained in the liquid 24 are adsorbed, the electrolytic solution 24 is circulated through the electrolytic solution circulation path that is returned to the electrolytic cell 20 through the discharge pipe 126. Thereby, the copper ion concentration in the electrolytic solution 24 in the electrolytic cell 20 is sufficiently reduced.

  In addition, in the other structural example which concerns on the anodizing surface treatment apparatus of the aluminum support illustrated in FIG. 2, the structure, operation | movement, and effect other than having demonstrated above are the anodizing surface treatment of the aluminum support shown in FIG. Since it is the same as the apparatus, its description is omitted.

  The configuration of the anodized surface treatment apparatus main body 10 provided with the copper ion remover 100 or the ion exchanger 120 according to the above-described embodiment is such that the supply of current is stopped in the anodized surface treatment step and the electrolytic reaction is predetermined. Means for suppressing copper deposition by stopping the contact between the aluminum support 12 and the electrolytic solution 24 by transferring the electrolytic solution 24 in the electrolytic cell 20 to the storage tank 40 when the operation is stopped over a threshold time. It may be attached together.

  In this case, when the controller (not shown) determines that the time for stopping the processing of the aluminum support 12 is equal to or longer than a predetermined threshold time (for example, 30 minutes), the conveyance of the aluminum support 12 is stopped and the direct current is stopped. The power supply 30 is turned off, the current supply from the DC power supply 30 to the electrodes 26 and 28 is interrupted, and a control operation for stopping the operation of the main pump 44 is performed.

  Thereby, in the surface treatment apparatus 11, the supply of the electrolytic solution 24 from the liquid storage tank 40 to the electrolytic tank 20 is stopped, and the electrolytic solution 24 in the electrolytic tank 20 is discharged from the return pipe 34 into the liquid storage tank 40. Since all the electrolytic solution 24 in the electrolytic cell 20 is discharged to the storage tank 40 and the electrolytic cell 20 is emptied (for example, drainage is completed in about 5 minutes), the electrolytic solution in the electrolytic cell 20 The aluminum support 12, the guide roller 16, etc. that have been immersed in 24 are detached from the electrolytic solution 24, and copper contact can be suppressed by cutting off contact with the electrolytic solution.

  Next, the Example concerning the surface treatment apparatus of the aluminum support body of this invention is described. In this embodiment, the anodized surface treatment apparatus main body 10 provided with the copper ion remover 100 shown in FIG. 1 is used.

Here, an anodizing treatment was performed using an aluminum support 12 having the following copper content using an electrolytic bath 20 which is an anodizing bath having an electrolytic solution capacity of 60 m ³ .

The implementation conditions at this time are:
Electrolyte capacity: 60m ³
Removal tank capacity of the copper ion remover 100: 200L,
Liquid flow rate into the removal tank: 70 L / min,
Cathode metal: Aluminum,
Anode metal: iridium oxide,
Aluminum area: 25m ²
Current: 14 A.
First, an anodizing treatment was performed without using the copper ion remover 100 using a 150 ppm copper-containing aluminum material.
As a result, the copper ion concentration in the electrolytic solution 24 was 5.6 ppm.

Second, 250 ppm of copper-containing aluminum material was used, and anodization was performed without using the copper ion remover 100.
As a result, the copper ion concentration in the electrolytic solution 24 was 11.0 ppm.

Third, 250 ppm of copper-containing aluminum material was used, and anodization was performed using the copper ion remover 100.
As a result, for example, after 3 to 4 hours, the copper ion concentration in the electrolyte solution 24 was reduced to 4.6 ppm.

  From the above, when the amount of copper contained in the aluminum support 12 is large, the copper ion concentration increases unless the copper ion remover 100 is used, whereas the copper ion concentration is decreased by operating the copper ion remover 100. It was confirmed that it was possible.

  Thus, if the copper ion concentration of the electrolytic solution 24 stored in the electrolytic cell 20 is constantly reduced using the copper ion remover 100, the processing operation is interrupted in the anodizing surface treatment process, and current is supplied. Even when is stopped and the electrolytic reaction is stopped, the amount of copper deposition can be suppressed.

  Therefore, when a CT plate is manufactured using the aluminum support 12 anodized by the anodized surface treatment apparatus main body 10 in which the copper ion concentration in the electrolytic solution 24 is sufficiently lowered by the copper ion remover 100 as a support. Since the metallic copper can be prevented from adhering to the surface of the aluminum support 12 before the photopolymer is applied, the photopolymer darkly polymerizes due to the influence of the metallic copper and the spot-like residue is left on the image forming surface of the CT plate. It can prevent that a film | membrane is produced | generated.

  In addition, although the surface treatment apparatus for an aluminum support according to the above-described embodiment has been described as performing an electrochemical surface treatment (anodizing treatment) by an in-liquid power feeding method, the aluminum support of the present invention has been described. The body surface treatment method and apparatus are not limited to this. For example, a method of supplying power by directly contacting an electrode with an aluminum support may be adopted.

  Moreover, the surface treatment method and apparatus for an aluminum support of the present invention allows a strip of aluminum or an alloy thereof to run in an electrolytic solution, and energizes the strip with an electrode provided in the electrolytic solution. It can be used for anodizing.

  Furthermore, since the surface treatment method and apparatus for an aluminum support of the present invention can be applied to an anodization performed in a liquid, in addition to the anodization of an aluminum support, an acid and electricity for the aluminum support can be applied. It can be applied to the used electropolishing treatment (nitric acid electrolysis, hydrochloric acid electrolysis, etc.).

It is a block diagram which shows the whole schematic structure of the surface treatment apparatus of the aluminum support body which concerns on embodiment in the surface treatment method and apparatus of the aluminum support body of this invention. It is a block diagram which shows the whole schematic structure of the other structural example in the surface treatment apparatus of the aluminum support body which concerns on embodiment in the surface treatment method and apparatus of the aluminum support body of this invention. It is a block diagram which illustrates the structure of the surface treatment apparatus of the conventional aluminum support body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Anodizing surface treatment apparatus main body 12 Aluminum support body 16 Guide roller 18 Feed tank 20 Electrolytic tank 22 Feed liquid 24 Electrolytic solution 26 Feed electrode 28 Electrolytic electrode 30 DC power supply 100 Copper ion remover 102 Liquid storage tank 104 Metal piece member 106 Metal Single member 108 DC power supply 110 Discharge pipe 112 Open / close valve 114 Inlet pipe 116 Discharge pipe 120 Ion exchanger 122 Introductory pipe 124 Liquid feed pump 126 Discharge pipe

Claims (7)

  A surface treatment method for an aluminum support characterized in that the copper ion concentration in the electrolytic solution is reduced by recovering copper ions from the electrolytic solution in an electrolytic cell in which an aluminum support is energized to perform anodization surface treatment . An electrolytic cell for storing an electrolyte solution;
Transport means for transporting the long aluminum support while being immersed in the electrolyte stored in the electrolytic cell;
In the electrolytic solution in the electrolytic cell, an electrode member arranged to face the aluminum support,
Power supply means for supplying a current to the electrode member to cause an electrolytic reaction between the electrode member and the aluminum support;
Copper ion removal means for removing copper ions in the electrolytic solution, which is disposed in the middle of the electrolytic solution circulation path after extracting the electrolytic solution from the electrolytic cell and returning it to the electrolytic cell again,
A surface treatment apparatus for an aluminum support, comprising:   The surface treatment of an aluminum support according to claim 2, wherein the copper ion removing means is a copper ion removing tank in which an electrolytic solution is stored and a metal member having a larger ionization tendency than copper is immersed. apparatus.   The surface treatment apparatus for an aluminum support according to claim 3, wherein a discharge port for discharging precipitated copper is provided at the bottom of the copper ion removal tank.   4. The aluminum support according to claim 2, wherein a cathode of a power source is connected to the metal member, and an anode of the power source is connected to an insoluble conductive member immersed in an electrolytic solution to flow an electric current. Surface treatment equipment.   The surface treatment apparatus for an aluminum support according to claim 2, wherein the copper ion removing means is a filter formed of a metal member having a higher ionization tendency than copper.   The surface treatment apparatus for an aluminum support according to claim 2, wherein the copper ion removing means is made of an ion exchange resin that adsorbs copper ions.

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