JP2015155563A - Apparatus and method for continuous electrolytic plating, metalized resin film and production method of the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for continuous electrolytic plating which can improve smoothness of a plated surface efficiently by simple means.

SOLUTION: In last electrolytic cells C11 and C12 highest in the set current density, among a plurality of electrolytic cells, there is provided a throttle shield plate 9a consisting of a shield plate 10 which extends in one direction and has a cross section U-shaped in the extension direction, with surfaces mutually in parallel in the extension direction being nearly rectangular, and a movable plate 11 attached to at least one surface of the nearly rectangular surfaces of the shield plate 10 so as to be swingable with 0-2° with respect to the shield plate 10 with the support point 12 as the center. The region shielding a to-be-treated article F1 is adjusted so as to be wide in the upper end part close to the liquid surface LL of the plating solution 5 and become narrow in the lower end part far from the liquid surface LL of the plating liquid 5.

COPYRIGHT: (C)2015,JPO&INPIT

Description

  The present invention relates to a metallized resin film used as a base material of a wiring material, and electroplating to an object to be processed such as a resin film with a metal thin film or a metal strip, which is used for producing the metallized resin film. The present invention relates to a continuous electroplating apparatus and method for applying the above.

  Metalized polyimide film, a type of metallized resin film, is widely used as a base material for wiring materials in electronic devices so that it can be made into a flexible printed wiring board (FPC) by wiring processing by subtractive method or semi-additive method. It is used.

  Currently, liquid crystal displays (LCDs), mobile phones, digital cameras, and other electronic devices are required to be thinner, smaller, lighter, and lower in cost. Is required. As a result, the wiring pitch of the FPC that is the wiring material is also narrower. Particularly in LCD driver wiring boards and the like, the finer wiring pitch is remarkable, and COF (Chip on film), which is an FPC capable of fine pitch mounting, is used for mounting a driver IC chip for LCD. ing. As the wiring pitch is further refined, the metallized polyimide film as the base material of the wiring material is further required to smooth the surface of the metal layer.

  At present, in a metallized polyimide film, a two-layer metallized polyimide film in which a metal layer is directly laminated on a polyimide film without using an adhesive is becoming mainstream. As a method for obtaining a double-layer metallized polyimide film, as described in JP-A-2003-342787, the surface of the polyimide film is directly applied to the surface of the polyimide film using a dry plating method such as sputtering or vapor deposition. After laminating the (seed) layer and the metal thin film layer, there is a method of thickening the metal plating layer on the plating surface of the metal thin film layer by using a roll-to-roll continuous electrolytic plating method.

  At this time, it is known that in the electrolytic plating process, the amount of plating at the end portion is increased due to an increase in current density at the end portion of the plating surface. Also in the metallized resin film manufacturing process, when the metal plating layer is thickened using a continuous electrolytic plating method on a long resin film with a metal thin film, the amount of plating increases at the end of the plating surface. . For this reason, in the metallized resin film, an appearance abnormality called “bake” occurs at both ends where the current density increases, resulting in a decrease in gloss or uneven contact with the power supply roll due to unevenness of the plating surface. As a result, abnormal deposition on the power supply roll may occur, or the unevenness of the plating surface may become severe. Furthermore, the metallized resin film is wound up in a roll shape after continuous electrolytic plating. However, when the unevenness of the plated surface becomes severe, the metallized resin film may be misaligned, and it may be difficult to wind the long film.

In contrast, JP 2011-58057 A discloses that after a metal thin film layer is formed on one side of a long polyimide film by a dry plating method, the film is conveyed so that the width direction is substantially horizontal. It is described that a copper plating film layer is formed on a surface of a metal thin film layer by a wet plating method using a plurality of insoluble anodes (anodes) to increase the current density stepwise in the transport direction. Has been. Specifically, when forming a copper plating film layer, an insoluble anode in which a current density due to an applied current is 35 mA / cm ² or more among a plurality of insoluble anodes. A substantially rectangular shielding plate is disposed between the film and the film, and the width of the portion from the upper end of the insoluble anode to the position of at least 40 cm from the upper end to the lower end is 80% to 90% of the width of the copper plating layer. By controlling in this way, the smoothness of the thickness of the copper plating film layer is improved. For example, when a copper plating film layer having a width of 470 mm is formed, the difference between the maximum value and the minimum value of the film thickness of the copper layer can be suppressed to 0.5 μm or less.

  Further, although it is not a roll-to-roll type continuous electrolytic plating method, Japanese Patent Application Laid-Open No. 2006-316322 discloses electrolytic plating opposite to the anode electrode when a sheet-like resin film with a metal thin film is conveyed. In the region where the resin film with a metal thin film is stretched in the conveyance direction of the resin film with a metal thin film, and the cross section with respect to the stretching direction has an opening cross-sectional shape combining a V shape and a square A technique is described in which a jig is arranged to prevent current from concentrating on the end of the plating surface.

  In any of the techniques described in any of the documents, the edge shielding jig faces the film with the metal thin film so that the amount (covering amount) covering the plated surface of the resin film with the metal thin film is constant with respect to the transport direction. Installed. The edge shielding jig has a substantially rectangular shape parallel to the extending direction, and the edge shielding jig and the resin film with a metal thin film are installed so as to be parallel to each other.

  By the way, in the metallized resin film, the entire surface of one surface of the film is not plated, but portions having a certain width that are not plated are provided at both ends thereof. Furthermore, in the continuous electroplating method of the roll-to-roll method, in the process of continuously electroplating the metallized resin film, the amount of plating is increased step by step through a plurality of electroplating cells. However, at this time, the current density is generally set to be increased step by step every time the electrolytic plating cell is passed.

  For this reason, depending on the setting of the fogging amount, a convex portion may be formed at the end portion of the plating surface and a concave portion may be formed inside the convex portion. Further, the positional relationship between the convex portions and the concave portions depends on electrolytic plating conditions such as current density and plating thickness. Therefore, in the present situation, a desired plating thickness is ensured up to the vicinity of the end of the plating surface, the plating surface width is constant with respect to the longitudinal direction, and smoothness is obtained up to both ends. For this, it is necessary to finely adjust the mounting position of the edge shielding jig to the electroplating apparatus and change the fogging amount in units of electroplating cells.

  In addition, the apparatus similar to the apparatus which performs the continuous electrolytic plating described in Unexamined-Japanese-Patent No. 2003-342787 or Unexamined-Japanese-Patent No. 2011-58057 is copper foil, as described in Unexamined-Japanese-Patent No. 2004-99950. It is also used as a device that applies continuous electrolytic plating to metal strips such as steel strips.

JP 2003-342787 A JP 2011-58075 A JP 2006-316322 A Japanese Patent Laid-Open No. 2004-99950

  As described above, in the roll-to-roll continuous electrolytic plating method, even if the fog amount is adjusted for each electrolytic plating cell, the unevenness of the plated surface and the appearance abnormality have not been completely eliminated. Moreover, adjustment of the amount of fog requires time and labor, and this is one factor that hinders the productivity of the metallized resin film in the roll-to-roll type continuous electrolytic plating method.

  Then, an object of this invention is to provide the continuous electroplating method and continuous electroplating apparatus which improve the smoothness of a plating surface efficiently with a simple means. Moreover, an object of this invention is to provide the metallized resin film excellent in the smoothness of the electrolytic plating surface, and its manufacturing method.

  In order to achieve the above object, the inventors of the present invention as an edge shielding jig, the region for shielding the object to be processed is wide at the upper end near the liquid surface of the plating solution and narrow at the lower end far from the liquid surface. By using what was constituted in this way, it was confirmed that the smoothness of the plated surface can be improved efficiently, and the present invention has been completed.

  The present invention provides a plating layer, a plurality of power supply rolls disposed above the plating layer, a plurality of anodes disposed substantially vertically in the plating layer, and the plurality of anodes in the plating tank. A plurality of conveying rolls disposed below, and maintaining a long object to be processed in a substantially horizontal direction through the plurality of power supply rolls and the plurality of conveying rolls, and In the plating solution in the plating tank, the object to be processed is conveyed so as to be substantially parallel to each of the plurality of anodes, and is in contact with the plurality of anodes and a corresponding power supply roll among the plurality of power supply rolls. The present invention relates to a roll-to-roll type continuous electrolytic plating apparatus configured such that a plurality of electrolytic plating cells are configured with a plating surface of an object, and a metal plating layer is sequentially laminated on the plating surface of the object to be processed.

In particular, in the continuous electrolytic plating apparatus of the present invention, each of the plurality of electrolytic plating cells extends in the conveying direction of the workpiece, and has a U-shaped cross section with respect to the extending direction. A parallel surface has a substantially rectangular shape, and is arranged so as to cover both ends of the object to be processed, and a shielding plate that shields both ends of the object to be processed from at least a part of each of the plurality of anodes. The edge shielding jig provided is provided so that the fogging amount is 0 mm to 60 mm, and among the plurality of electrolytic plating cells, at least one electrolysis having a set current density of 3.0 A / dm ² or more. In the plating cell, at least on the surface of the edge shielding jig facing the anode, the region for shielding the object to be processed is wide at the upper end near the liquid surface of the plating solution and narrow at the lower end far from the liquid surface. Configured In the edge shielding jig having the inclined portion, the maximum fogging amount at the upper end portion of the edge shielding jig is larger than the fogging amount of the edge shielding jig not having the inclined portion, and is 100 mm or less. It is provided.

  It is preferable that the edge shielding jig provided with the inclined portion is installed in an electroplating cell having the highest set current density. In general, the electrolytic plating cell having the highest set current density is the last electrolytic plating cell among the plurality of electrolytic plating cells.

  In such a continuous electrolytic plating apparatus according to the present invention, the edge shielding jig including the inclined portion includes at least one of the shielding plate and the substantially rectangular surface of the shielding plate facing the anode. And a movable plate attached so as to be rotatable about a fulcrum provided on the side far from the liquid level of the liquid, and the movable plate rotates with respect to the shield plate. The inclined portion is preferably formed. The movable plate is preferably rotatable with respect to the shielding plate in a range of at least 0 ° to 2 °.

  The continuous electrolytic plating method of the present invention uses the continuous electrolytic plating apparatus of the present invention, and the width direction of the long object to be processed is substantially horizontal via the plurality of power supply rolls and the plurality of transport rolls. In the plating solution in the plating tank, while being kept in the direction, it is conveyed so as to be substantially parallel to each of the plurality of anodes, and the plurality of anodes and the corresponding power supply among the plurality of power supply rolls A roll-to-roll type continuous electrolytic plating method in which a plurality of electrolytic plating cells are configured with the plating surface of the workpiece to be in contact with the roll, and a metal plating layer is sequentially laminated on the plating surface of the workpiece. .

In particular, in the continuous electrolytic plating method of the present invention, the plurality of electrolytic plating cells extend in the conveying direction of the workpiece, and have a U-shaped cross section with respect to the extending direction. A parallel surface has a substantially rectangular shape, and is arranged so as to cover both ends of the object to be processed, and a shielding plate that shields both ends of the object to be processed from at least a part of each of the plurality of anodes. The edge shielding jig provided is installed so that the fogging amount is 0 mm to 60 mm, and among the plurality of electrolytic plating cells, at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more Further, at least the surface of the edge shielding jig facing the anode is configured such that a region for shielding the object to be processed is wide at the upper end near the liquid surface of the plating solution and narrow at the lower end far from the liquid surface. Was In the edge shielding jig provided with the inclined portion, the maximum fogging amount at the upper end portion of the edge shielding jig is larger than the fogging amount of the edge shielding jig not provided with the inclined portion, and 100 mm or less. It is characterized by installing.

  It is preferable to install the edge shielding jig provided with the inclined portion in at least an electrolytic plating cell having the highest set current density. Normally, the last electrolytic plating cell among the plurality of electrolytic plating cells is an electrolytic plating cell having the highest set current density.

  In the case of using an edge shielding jig provided with the inclined portion, the opening portion of the inclined portion is preferably set to 0.5 ° to 2 °.

  The method for producing a metallized resin film according to the present invention includes a base metal film forming step of forming a base metal layer on at least one surface of an insulating resin film by a dry plating method without using an adhesive, and a dry process on the base metal layer. Metallization comprising a dry plating process in which a copper thin film layer is laminated by a plating method to form a resin film with a metal thin film, and an electroplating process in which a copper plating layer is laminated on the resin film with a metal thin film by electrolytic plating It is a manufacturing method of a resin film, Comprising: The said electrolytic plating process uses the continuous electrolytic plating method of this invention which uses this resin film with a metal thin film as the said to-be-processed object.

  The metallized resin film of the present invention is obtained by the method for producing a metallized resin film of the present invention, and the difference between the maximum value and the minimum value of the film thickness distribution in the width direction of the copper plating layer is 0. It is characterized by being 25 μm or less.

The edge shielding jig of the present invention has a shielding plate that extends in one direction, has a U-shaped cross section with respect to the stretching direction, and has a substantially rectangular shape in parallel to the stretching direction. Comprising a movable plate attached to at least one of the substantially rectangular surfaces so as to be rotatable in a range of 0 ° to 2 ° with respect to the shielding plate, with a fulcrum as a center, and constitutes a continuous electrolytic plating apparatus. In at least one electrolytic plating cell having a set current density of 3.0 A / cm ² or more, a throttle shielding plate is installed so as to cover both ends of the workpiece to be conveyed substantially parallel to the anode of the electrolytic plating cell Consists of.

  According to the continuous electrolytic plating method and the continuous electrolytic plating apparatus of the present invention, the fogging amount is large at the end portion near the liquid surface of the plating solution of the edge shielding jig, and the covering amount is small at the end portion far from the liquid surface of the plating solution. This is achieved efficiently by simple means, and the smoothness of the plated surface can be improved as compared with the prior art. Further, according to the present invention, it is possible to adjust the fog amount in a very short time. Furthermore, by applying the present invention to the electroplating process of the metallized resin film, the smoothness of the electroplating surface is improved, and not only is it extremely useful for the finer wiring pitch of the flexible wiring board, Productivity can be greatly improved. For this reason, the industrial significance of the present invention is extremely large.

FIG. 1 is a schematic view of a continuous electrolytic plating apparatus to which the present invention is applied. FIG. 2 is an explanatory view of an electrolytic plating cell using a shielding plate having a U-shaped cross section. FIG. 3 is an explanatory view similar to FIG. 2 for an electroplating cell using a shielding plate with a movable plate having a U-shaped cross section. FIG. 4 is a schematic diagram of a shielding plate with a movable plate having a U-shaped cross section and a cover amount. FIG. 4A is a plan view when the movable plate is stored, FIG. 4 (b) is a front view when the movable plate is stored, FIG. 4 (c) is a plan view when the movable plate is deployed, and FIG. 4 (d) is a front view when the movable plate is deployed.

  Hereinafter, the present invention will be described by being divided into “1. Continuous electrolytic plating apparatus and continuous electrolytic plating method” and “2. Manufacturing method of metallized resin film and metallized resin film”. In the following, a case where electrolytic plating is applied to a resin film with a metal thin film is described as an example. However, the present invention is not limited to this, for example, a metal such as a copper foil or a copper strip. Any material that can be transported in a roll-to-roll manner, such as a strip, and can provide electrical continuity between the surface that contacts the power supply roll and the surface that faces the anode Applicable.

1. Continuous Electroplating Apparatus and Continuous Electroplating Method (1) Basic Configuration FIGS. 1 to 4 show a continuous electroplating apparatus 1 that is an example of an embodiment of the present invention. As shown in FIG. 1, the basic structure of the continuous electrolytic plating apparatus 1 is the same as that of the prior art. The metal film with metal thin film F1, which is a long object to be treated, is unwound from an unwinding roll 2, and this metal The thin film-attached resin film F1 is conveyed while maintaining the width direction in a substantially horizontal direction, and is plated in a plating tank 4 having a plurality of anodes (anodes) 6a to 6l installed substantially perpendicular to the liquid level LL. While being immersed in the liquid 5 and transporting the anodes 6a to 6l so as to face each of the anodes 6a to 6l, electrolytic plating is performed by a plurality of electrolytic plating cells C1 to C12, and the metal thin film layer of the resin film F1 with a metal thin film This is a roll-to-roll system apparatus in which the metal plating layer 14 is sequentially laminated on the plating surface to obtain a metallized resin film F <b> 2 and is wound around the winding roll 3. Here, “substantially horizontal”, “substantially vertical” or “substantially parallel” not only means completely horizontal, vertical or parallel, but also transport of the resin film F1 with a metal thin film and a metal plating layer on the plating surface. As long as it does not affect the formation of 14, it means that even if not completely horizontal, vertical or parallel, it is allowed.

  In addition, in this example, the resin film F1 with a metal thin film is obtained by laminating a base metal layer and a metal thin film layer on at least one surface of the resin film without using an adhesive. Moreover, as a metal which forms the metal plating layer 14, there are metals and alloys to which electrolytic plating such as copper, gold, nickel, and zinc is applied, and as an object to be processed, in addition to the resin film with a metal thin film, at least There are metal strips such as copper foil and steel strip that are electroplated with the same kind of metal on one side.

  More specifically, the unrolled resin film F1 with a metal thin film is plated with a plurality of power supply rolls 7a to 7g and a plurality of transport rolls 8a to 8f while maintaining the width direction in a substantially horizontal direction. It is conveyed so that the immersion to 5 is repeated. In the meantime, the metal plating layer 14 is sequentially laminated | stacked on the resin film F1 with a metal thin film by electrolytic plating, and the obtained metallized resin film F2 is wound up by the winding roll 3. FIG. In addition, the continuous electrolytic plating apparatus 1 includes various known apparatuses used for transporting a long film such as a control roll for controlling the tension of the resin film F1 with a metal thin film or a metal strip, stirring of the plating solution 5, Various known devices used for supply and the like can be additionally installed.

  As the plating solution 5 and the anodes 6a to 6l, known ones can be used according to the metal plating layer 14 to be formed. For example, if copper electrolytic plating is performed, a known copper plating solution can be used, and the anodes 6a to 6l can also be made of a copper anode or a known insoluble anode. However, from the viewpoint of improving the film thickness distribution of the metal plating layer 14, it is preferable to use an insoluble anode. Further, the numbers of the anodes 6a to 6l, the power supply rolls 7a to 7g, and the transport rolls 8a to 8f can be arbitrarily determined as necessary.

  As shown in FIG. 1, a potential difference is generated between the resin film F1 with a metal thin film and the anodes 6a to 6l that are in contact with the power supply rolls 7a to 7g, thereby forming electrolytic plating cells C1 to C12. The anodes 6a to 6l are installed in the plating tank 4 through a frame (not shown). The upper ends of the anodes 6a to 6l are usually slightly above the liquid level LL of the plating solution 5, and the upper ends of the anodes 6a to 6l are more than the liquid level LL even if the liquid level is somewhat wavy. It arrange | positions so that it may not be located below. The anodes 6a to 6l may be configured by a single anode as shown in FIGS. 1 to 3, or may be divided into two in the vertical direction and configured by an upper anode and a lower anode.

  A power supply device (not shown) is individually connected to each of the anodes 6a to 6l, and the current densities of the electrolytic plating cells C1 to C12 can be individually set. In the case of a vertically divided anode, the current density in one electrolytic plating cell can be made more uniform by individually controlling the current of the upper anode and the lower anode.

  The current densities of the electroplating cells C1 to C12 may all be the same, but are usually controlled so as to increase stepwise along the transport direction of the resin film F1 with a metal thin film. For example, the continuous plating apparatus 1 shown in FIG. 1 may be configured to increase the current density continuously and stepwise from the anode 6a to the anode 6l in the order of the electrolytic plating cells C1 to C12. Further, the current density becomes the minimum value in the electroplating cells C1 and C2 of the anodes 6a and 6b, and the current density gradually increases in the electroplating cells C3 to C10 from the anode 6c to the anode 6j, so that the electrolysis of the anodes 6k and 6l is performed. It is also possible to control so that the current density becomes the maximum value in the plating cells C11 and C12.

(2) Edge shielding jig In the continuous electrolytic plating apparatus 1 as shown in FIG. 1, as described above, current tends to concentrate on both ends of the metal plating layer 14, and on both ends of the plating surface of the metal plating layer 14. The convex portion is formed with a concave portion on the inner side in the width direction. Further, in each of the electroplating cells C1 to C12, the current on the cathode side is supplied to the plating surface of the metal plating layer 14 by the power supply rolls 7a to 7g installed above the liquid surface LL of the plating solution 5. The current density also changes in the vertical direction. Generally, the current density is high in the vicinity of the liquid level LL near the power supply rolls 7a to 7g in the plating surface of the metal plating layer 14, and proceeds from the liquid level LL in the depth direction. As the current density gradually decreases, the current density tends to be lowest in the vicinity of the transport rolls 8a to 8f. In particular, this tendency becomes prominent in electrolytic plating cells having high current density (usually, electrolytic plating cells C11 and C12 on the downstream side (winding roll 3 side)). As a result, in the metallized resin film F2 finally obtained, the film thickness distribution of the metal plating layer 14 becomes wide not only in the width direction but also in the transport direction (longitudinal direction).

  Therefore, for example, when the technology described in JP-A-2006-316322 is applied and both ends of the resin film F1 with a metal thin film are shielded by an edge shielding jig, the film in the width direction of the resin film F1 with a metal thin film Even if variations in thickness distribution can be suppressed, it is extremely difficult to suppress variations in thickness distribution in the transport direction at the same time. That is, in order to suppress the variation in the film thickness distribution in the width direction and the conveyance direction at the same time by such an edge shielding jig, it is necessary to adjust the fogging amount of the edge shielding jig for each of the electrolytic plating cells C1 to C12. However, in order to perform this adjustment, a part of the plating solution 5 in the plating tank 4 must be discharged out of the tank and the position of the liquid level LL must be lowered. For this reason, in order to optimize the fogging amount of the edge shielding jig for each of the electrolytic plating cells C1 to C12, in addition to the adjustment time of the fogging amount of the edge shielding plate, filling and discharging of the plating solution 5 are performed. Time required is required, and productivity is significantly reduced.

On the other hand, in this invention, as shown in FIGS. 2-4, it extends to the electroplating cell C1-C12 in the conveyance direction of the resin film F1 with a metal thin film, and a cross section is U character with respect to the expansion | extension direction. The surfaces parallel to each other in the extending direction have a substantially rectangular shape, are arranged so as to cover both end portions of the resin film F1 with a metal thin film, and are shielded from at least a part of each of the plurality of anodes 6a to 6l. The edge shielding jig 9 comprising the shielding plate 10 is installed (FIG. 2), and among the electroplating cells C1 to C12, at least one electroplating cell having a set current density of 3.0 A / dm ² or more, As the edge shielding jig, the edge shielding jig 9 has a region where the resin film F1 with a metal thin film is shielded at least on the surface facing the anode at the upper end near the liquid surface LL of the plating solution 5. The edge shielding jig 9a to which an inclined portion configured to be narrow at the lower end far from the liquid level LL is added is installed instead of the edge shielding jig 9 (FIGS. 3 and 4). . The fogging amount of the edge shielding jig 9 and the edge shielding jig 9a having the inclined portion is controlled within a predetermined range. Here, the set current density refers to a current density set in advance in order to achieve a desired amount of electrodeposition, an area of an electroplating surface, and an electrodeposition time in each of the electroplating cells C1 to C12.

That is, in the present invention, in combination with the edge shielding jig 9, edge shielding is performed in at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more that affects the plating thickness of the plating surface of the metal plating layer 14. By using the edge shielding jig 9a having an inclined portion instead of the jig 9, the plating surface can be cut off corresponding to the current density distribution in the conveying direction as well as in the width direction. In industrial scale production, a metallized resin film F2 having high smoothness can be easily obtained. Moreover, in the present invention, such a uniform current density is realized mainly by adjusting the fogging amount of the edge shielding jig 9a provided with the inclined portion installed in the electrolytic plating cell having a high set current density. Therefore, the adjustment time can be reduced. In particular, when a throttle shielding plate, which will be described later, is employed as the edge shielding jig 9 a having an inclined portion, it is possible to adjust the fogging amount without discharging the plating solution 5 from the plating layer 4. The adjustment time can be greatly reduced.

  In addition, this invention can also be used together with the edge shielding jig | tool for adjusting the width | variety of anode 6a-6l as described in Unexamined-Japanese-Patent No. 2011-58057, The metallized resin obtained by this It becomes possible to further improve the smoothness of the plated surface of the film F2.

[Installation position]
As described above, in the present invention, the edge shielding jig 9a having an inclined portion is installed in at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more. The edge shielding jig 9 is installed. In all the electroplating cells C1 to C12, it is possible to install the edge shielding jig 9a having an inclined portion, but it is preferable to install it in an electroplating cell having a higher set current density. In particular, the last electrolytic plating cell C12 or C11 and C12 on the most downstream side (winding roll 3 side) is adjusted so as to be an electrolytic plating cell having the highest set current density, and this electrolytic plating cell C12 or C11. It is preferable to install an edge shielding jig 9a having an inclined portion at C12. With such a configuration, not only the electrodeposition behavior in an electrolytic plating cell having a high set current density, which affects the plating thickness of the plating surface of the metal plating layer 14 of the resin film F1 with a metal thin film, is appropriately controlled, but also substantially In particular, the adjustment of the fogging amount has only to be performed on the edge shielding jig 9a having the inclined portions installed in the electrolytic plating cells C11 or C11 and C12, so that the adjustment time is shortened and the metal resin film is obtained. It is also possible to improve the productivity of F2.

  The electrodeposition by electrolytic plating is performed on the entire surface where the resin film F1 with a metal thin film is immersed in the plating solution 5. In addition, the current density is greatest in the vicinity of the liquid level LL of the plating solution 5. For this reason, in the electrolytic plating cells C1 to C12, the edge shielding jig 9 and the edge shielding jig 9a are preferably arranged at least from the position of the liquid level LL of the plating solution 5, and above the liquid level LL of the plating solution 5 It is more preferable to arrange so as to protrude. Further, the height (length in the longitudinal direction) of the edge shielding jig 9 and the edge shielding jig 9 provided with the inclined portion is the length of the portion extending downward from the position of the liquid level LL of the plating solution 5, that is, The length of the portion immersed in the plating solution 5 is preferably 70% or more of the distance from the position of the liquid level LL of the plating solution 5 to the rotation shaft of the transport rolls 8a to 8f, and is 95% or more. It is more preferable.

[Mode of edge shielding jig]
The shielding plate 10 constituting the edge shielding jig 9 and the edge shielding jig 9a having an inclined portion of the present invention extends in the conveying direction of the resin film F1 with a metal thin film, and has a U-shaped cross section with respect to the extending direction. The surfaces parallel to each other in the extending direction have a substantially rectangular shape. Here, “substantially rectangular” means that the shape of the surfaces parallel to the extending direction of the shielding plate 10 is a perfect rectangle, as long as both ends of the resin film F1 with a metal thin film can be shielded. Including cases that are not completely rectangular. Thus, when the shape of the cross section of the shielding plate 10 is U-shaped, it is possible to prevent the wraparound of electricity (plating adherend) from the side surface and the back surface, and smoothness of the resulting metallized resin film F1. Can be improved.

  Note that the width of the shielding plate 10 may be appropriately set according to the characteristics of the electroplating apparatus to be used as long as the fogging amount D to be described later can be secured, but as an example, the width can be about 50 mm to 150 mm. . In addition, the interval between the opposing inner surfaces should be as narrow as possible in order to suppress wraparound of electricity. However, if this interval is too narrow, there is a risk of interference with the shielding plate 10 during the transport of the resin film F1 with a metal thin film. For this reason, when performing a plating process with respect to the resin film F1 with a metal thin film of thickness about 10 micrometers-100 micrometers, it is preferable that the space | interval of the inner surface which the shielding board 10 opposes shall be about 20 mm-50 mm.

  Further, the edge shielding jig 9 and the edge shielding jig 9a having an inclined portion are made of a well-known electrically insulating plastic or ceramic used for a conventional edge shielding jig, and are formed by plastic bending or injection molding, ceramic. The thickness is preferably about 2 mm to 5 mm.

In the present invention, particularly in at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more, a resin with a metal thin film is provided on at least the surface of the edge shielding jig 9 facing the anode as the edge shielding jig. It is necessary to use an edge shielding jig 9a having an inclined portion configured such that the region shielding the film F1 is wide at the upper end portion near the liquid level LL of the plating solution 5 and narrows at the lower end portion far from the liquid level LL. There is. As an example of the edge shielding jig 9a having such an inclined portion, a throttle shielding plate shown in FIGS. 3 and 4 will be described below.

  The throttle shielding plate 9a includes a shielding plate 10 similar to the edge shielding jig 9, and has a configuration in which a movable plate 11 is attached to the surface of the shielding plate 10 facing the anode. In this example, the movable plate 11 is also made of a known electrically insulating plastic or ceramic and has the same width as the shielding plate 10. At this time, the lower end portion of the movable plate 11 is attached to the feeding roll 7 g side of the shielding plate 10, and the upper end portion of the movable plate 11 is extended so as to protrude upward from the liquid level LL of the plating solution 5. preferable. Thereby, it is possible to sufficiently secure the fogging amount D in the vicinity of the liquid level LL of the plating solution 5 in which the current density becomes relatively high.

  Further, the height (length in the longitudinal direction) of the movable plate 11 is such that the length of the portion extending downward from the position of the liquid level LL of the plating solution 5 is from the position of the liquid level LL of the plating solution 5 to the transport roll 8f. The distance to the rotation axis is set to be 40% or more, preferably 70% or more, but may be the same shape and size as the surface of the throttle shielding plate 9a facing the anode 6l. More specifically, when the height of the throttle shielding plate 9a is 1000 mm, the height of the movable plate 11 is 50% to 100%. If the height of the movable plate 11 falls below 40% of the distance of the rotation axis of the transport roll 8f from the position of the liquid level LL of the plating solution 5, the amount of fogging at the center of the electrodeposition region from the liquid surface to the transport roll Since the adjustment effect of D decreases, the effect of the movable plate 11 may not be obtained.

  Furthermore, the movable plate 11 is on the side of the transport roll 8f opposite to the liquid level LL of the plating solution 5 and on the opposite side of the portion covering the resin film F1 with a metal thin film (both ends on the lower end portion; FIG. 4). In (b) and (d), the fulcrum 12 is located on the lower left side) on the side of the power supply roll 7g close to the liquid level LL of the plating solution 5 and the corner opposite to the portion covering the resin film F1 with metal thin film ( Long holes 13 are respectively provided on both ends of the upper end portion; on the upper left side in FIGS. 4B and 4D.

  The movable plate 11 is pivotally supported by the shielding plate 10 at a fulcrum 12 by a fixing jig (not shown) such as a screw. For this reason, the throttle shielding plate 9a has a metal plate on at least the surface of the edge shielding jig facing the anode by rotating the movable plate 11 around the fulcrum 12 in a direction covering the resin film F1 with a metal thin film. An inclined portion configured to cover the thin resin film F1 with a thin film is wide at the upper end near the liquid level LL of the plating solution 5 and narrow at the lower end far from the liquid level LL of the plating solution 5. It is possible to form.

  In addition, it is preferable that the movable plate 11 can be fixed at an arbitrary position through a long hole 13 by a fixing jig (not shown) such as a screw. More preferably, it is provided above the liquid level LL of the liquid 5. By adopting such a configuration, it is possible to adjust the fogging amount D without discharging the plating solution 5 in the plating layer 4 to the outside of the tank, so that the adjustment time can be greatly shortened. .

  Further, the rotation range of the movable plate 11 is not particularly limited, but at least with respect to the shielding plate 10, the opening angle α of the movable plate 11 at the time of electrolytic plating can be adjusted within a range described later. It is preferable to be able to rotate in the range of 0 ° to 2 °.

As described above, the throttle shielding jig has been described as an example of the edge shielding jig 9a having the inclined portion. However, in the present invention, the fogging amount D of the portion where the current density is high becomes relatively large, and the portion where the current density is low. As long as the fogging amount D can be relatively reduced, various types of edge shielding jigs having inclined portions can be employed. For example, the pair of shielding plates 10 face each other. Of the inner surface, the portion from the middle part to the upper plate part may be configured to incline toward each other, and the movable plate 11 may be omitted. Further, the shape of the inner side surfaces of the pair of movable plates 11 respectively attached to the pair of shielding plates 10 facing each other can be a shape other than a straight line such as a stepped shape or a substantially arc shape. However, the above-described configuration of the throttle shielding plate 9a is a simple means that simply attaches the rotatable movable plate 11 to the shielding plate 10, is easy to manufacture, and has a high degree of freedom of adjustment. Therefore, it can be said that it is preferable. However, the set current density is less than 3.0 A / dm ^{2 in the same} manner as the setting of the fogging amount D, regardless of the form of the edge shielding jig 9 a having the inclined portion. In the electrolytic plating cell, it is necessary to pay attention so that the maximum fogging amount Dmax described later is not set excessively.

[Cover amount]
The edge shielding jig 9a and the edge shielding jig 9a provided with the inclined portion are such that at least the surface facing the anodes 6a to 6l exceeds the non-plating portions at both ends of the resin film F1 with a metal thin film, and the inner metal plating layer 14 is provided so as to cover the plated surface of 14, and a region overlapping the plated surface of the metal plated layer 14 is provided. The dimension in the width direction of this region is defined as the fogging amount D, and the area of this region is defined as the fogging area. The edge shielding jig 9 and the edge shielding jig 9a having an inclined portion preferably have a structure in which the fogging amount D can be adjusted by finely adjusting the attachment position to the electroplating apparatus 1, such as current density. It is possible to improve the smoothness of the metal plating layer 14 by adjusting the fogging amount D according to the electrolytic plating conditions and plating thickness. In addition, in the edge shielding jig 9a including the edge shielding jig 9 and the inclined portion, the resin film F1 with a metal thin film is used so as not to interfere with the attachment to the electroplating apparatus 1 within a range that does not affect the fogging amount D. It is not hindered to provide notches, protrusions, etc. on a substantially rectangular surface parallel to the surface.

  More specifically, an edge shielding jig 9 and an edge shielding jig 9a having an inclined portion are installed so as to cover both ends of the resin film F1 with a metal thin film facing each of the anodes 6a to 6l. The fogging amount D of the shielding plate 10 is the sum of the fogging amounts D at both ends, and can be adjusted in the range of 0 mm to 60 mm, preferably 10 mm to 60 mm. If the cover amount D of the shielding plate 10 is set excessively, the plating surface of the metal plating layer 14 cannot be set to a desired width, the film thickness cannot be made sufficient, or plating is performed. There are cases where the surface cannot be made sufficiently smooth. In the present invention, the fogging amount D of the shielding plate 10 should be set individually for each of the electroplating cells C1 to C12 according to conditions such as a set current density. For this reason, especially in an electroplating cell having a small set current density, the width, film thickness and smoothness of the plating surface of the metal plating layer 14 can be sufficiently ensured without installing the shielding plate 10. In such a case, the fogging amount D of the shielding plate 10 can be set to zero.

Further, in the edge shielding jig 9a having an inclined portion that is disposed in at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more, the amount of fog in the vicinity of the liquid surface LL having a high current density (hereinafter referred to as “the current density”) It is necessary to relatively reduce the fogging amount (hereinafter referred to as “minimum fogging amount”) Dmin in the vicinity of the transport roll 8f having a relatively large Dmax and a low current density. Thereby, at both ends of the metal plating layer 14, the range shielded by the edge shielding jig 9a having the inclined portion can be changed according to the current density, and the amount of electrodeposition can be adjusted. In addition, the current density of the plating surface of the metal plating layer 14 in the vicinity of the liquid surface LL of the plating solution 5 can be suppressed, and the occurrence of burns or the like can be prevented.

  In particular, when the above-described throttle shielding plate is used as the edge shielding jig 9a having an inclined portion, the maximum fogging amount Dmax can be easily set with a high degree of freedom by adjusting the opening angle α of the movable plate 11. Since it can control, it becomes possible to improve the smoothness of the plating surface of the metal plating layer 14 significantly. Here, the opening angle α of the movable plate 11 refers to the rotation angle of the movable plate 11 with respect to the shielding plate 10 during electrolytic plating (see FIG. 4D).

  More specifically, the throttle shielding plate 9a is installed in the electroplating cell C12 having the highest set current density, and the resin film F1 with a metal thin film having an overall width of 520 mm and a plating surface width of the metal plating layer 14 of 500 mm is electrolyzed. In the case of plating, by adjusting the opening angle α of the movable plate 11, the maximum fogging amount Dmax is larger than the fogging amount D (0 mm to 60 mm) of the edge shielding jig and 100 mm or less, preferably edge shielding. It is necessary to control it to be about 10 mm larger than the fogging amount D of the jig and 100 mm or less. When the maximum fogging amount Dmax exceeds 100 mm, the amount of electrodeposition at the upper end of the throttle shielding plate 9a is excessively limited, and the plated surface cannot be made sufficiently smooth.

  The opening angle α of the movable plate 11 at the time of electrolytic plating is preferably 0.5 ° to 2 °, more preferably 1 ° to 2 although it depends on conditions such as the position where the movable plate 11 is attached and the current density. More preferably, it is controlled in the range of 1 ° to 1.5 °. If the opening angle α is less than 0.5 °, the effect of providing the movable plate 11 may not be sufficiently obtained. On the other hand, if the opening angle exceeds 2 °, the maximum fogging amount Dmax becomes too large, and the necessary electrodeposition amount may not be obtained.

  Further, in the slot shielding plate 9a, the fog amount D when the opening angle α of the movable plate 11 is 0 °, that is, the fog amount D of the shielding plate 10 constituting the throttle shielding plate 9a is as described above. The total amount of fogging D of the part is in the range of 0 mm to 60 mm, preferably 10 mm to 60 mm. However, the amount of fog D is not necessarily the same as the amount of fog D of the shielding plate 10 constituting the edge shielding jig 9, and can be adjusted as appropriate in consideration of the amount of fog by the movable plate 11. preferable.

2. Metallized Resin Film Manufacturing Method and Metallized Resin Film (1) Metallized Resin Film Manufacturing Method The continuous electrolytic plating method of the present invention can be suitably applied to the electrolytic plating process of the metallized resin film F2. The manufacturing method of the metallized resin film F2 is, in order, a base metal film forming step of forming a base metal (seed) layer by dry plating on at least one surface of the insulating resin film without using an adhesive, and a base metal layer A dry plating process for laminating a copper thin film layer by dry plating, and an electroplating process for laminating a copper plating layer on the plated surface of the copper thin film layer by supplying power through the base metal layer and the copper thin film layer. Prepare.

  In this way, the metallized resin film F2 having the copper plating layer formed thereon is subjected to patterning by a semi-additive method or a subtractive method, and is widely used as a wiring material in electronic equipment as a flexible printed wiring board. The

[Base metal film formation process]
Examples of the insulating resin film used as the base material of the metallized resin film F2 include polyimide films, polyamide films, polyester films, polytetrafluoroethylene films, polyfinylene sulfide films, polyethylene naphthalate films, and liquid crystal polymers. Although resin films, such as a system film, are mentioned, a polyimide system film is suitable at the point applicable also to the use which requires high temperature connections, such as solder reflow. For use as a wiring material, an insulating resin film having a thickness of about 8 μm to 75 μm is suitable.

  As the material for the base metal layer, nickel or an alloy containing nickel is preferably used. Moreover, it is also possible to add another metal in order to improve corrosion resistance. As the additive metal, chromium, vanadium, titanium, molybdenum, cobalt, tungsten, or the like can be used.

  The dry plating method used in the step of forming the base metal layer is not particularly limited, but is preferably any one of a vacuum deposition method, a sputtering method, and an ion plating method, and more preferably a sputtering method. For example, when forming a base metal layer using a winding-type sputtering apparatus, an alloy target having a desired base metal layer composition is attached to a sputtering cathode, an insulating resin film is set, and the inside of the apparatus is evacuated. Then, argon gas is introduced and the apparatus is held at about 0.13 Pa to 1.3 Pa, and power is supplied from a DC power source for sputtering connected to the cathode, and sputtering discharge is performed on the insulating resin film. A desired base metal layer can be continuously formed. Moreover, you may perform well-known various processes, such as a plasma process, an ultraviolet irradiation process, a corona discharge process, an ion beam process, a fluorine gas process, before performing dry plating.

  The thickness of the base metal layer is preferably 3 nm to 50 nm. If the thickness of the underlying metal layer is less than 3 nm, the metal coating layer (underlying metal layer, copper thin film layer, copper plating layer) other than the wiring portion is removed by etching or the like, and finally the wiring is etched. The liquid may erode the base metal layer, soak into the insulating resin film and the base metal layer, and the wiring may float. On the other hand, if the thickness of the base metal layer exceeds 50 nm, when the wiring is finally produced by etching or the like, the base metal layer is not completely removed and remains as a residue between the wirings. May occur.

[Dry plating process]
The copper thin film layer can be formed by a dry plating method using a sputtering apparatus in which a copper target is mounted on a sputtering cathode, similarly to the manufacturing process of the base metal layer. In this case, it is preferable to continuously form the base metal layer and the copper thin film layer in the same vacuum chamber. Although the film thickness of a copper thin film layer is not specifically limited, It is preferable that they are 10 nm-0.3 micrometer. If the film thickness of the copper thin film layer is less than 10 nm, it is not preferable because the conductivity is low and a sufficient power supply amount cannot be secured when performing the electrolytic copper plating process. On the other hand, when the film thickness of the copper thin film layer exceeds 0.3 μm, productivity at the time of film formation decreases, which is not preferable.

[Electrolytic plating process]
The metallized resin film F2 of the present invention is formed by laminating a copper plating layer on the copper thin film layer of the insulating resin film F1 with a copper thin film by the continuous electrolytic plating method of the present invention. Except that the continuous electrolytic plating method of the present invention is used, the conditions of the electrolytic plating method are not particularly limited, and various known conditions are adopted for the configuration of the plating bath, the current density, the conveyance speed, and the like. Can do.

  The film thickness of the copper film formed by combining the copper thin film layer formed on the base metal layer and the copper plating layer formed on the copper thin film layer by the electrolytic plating method is manufactured using a two-layer flexible substrate. Although it is appropriately set according to the manufacturing method of the printed wiring board, it is generally preferable to set the thickness to 0.5 μm to 18 μm. There are mainly semi-additive and subtractive methods for manufacturing printed wiring boards, but the semi-additive method uses a two-layer flexible substrate with a relatively thin copper coating, while the subtractive method Two-layer flexible substrates having a relatively thick copper coating are used. When the film thickness of the copper coating is less than 0.5 μm, it is not preferable because it becomes difficult to form a copper plating layer by an electroplating method when wiring is formed by a semi-additive method. Further, when the film thickness is larger than 18 μm, it is not preferable because the etching time becomes long and the productivity is lowered when the wiring is formed by the subtractive method.

(2) Metalized resin film According to the manufacturing method of the metallized resin film F2 to which the continuous electrolytic plating method of the present invention is applied, the film thickness in the film thickness distribution over the width direction of the copper film of the metallized resin film F2 obtained. The difference between the maximum value and the minimum value can be 0.25 μm or less, preferably 0.20 μm or less. Thus, the smoothness of the plated surface of the copper coating layer can be further improved as compared with the conventional method by the continuous electrolytic plating method of the present invention and the manufacturing method of the metallized resin film F2 using the same.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited at all by these Examples.

Example 1
Using a continuous electrolytic plating apparatus 1 having the same configuration as that shown in FIG. 1, a metal thin film is formed on a polyimide film F1 with a metal thin film in which a base metal layer and a copper thin film layer are laminated on one side of a polyimide film by sputtering. Copper was laminated | stacked on the layer by continuous electrolytic plating, and the metallized polyimide film F2 provided with the copper plating layer was manufactured. In addition, the polyimide film (Thickness 38micrometer, width 524mm, brand name: 150EN-F) by Toray DuPont Co., Ltd. was used for the polyimide film. Further, as the base metal layer, a nickel alloy thin film layer (film thickness 7.5 nm) containing 7% by mass of chromium is formed, and a copper thin film layer (film thickness 100 nm) is formed on the nickel alloy thin film layer. Formed. The width of the base metal layer and the copper thin film layer was 510 mm.

  As the anodes 6a to 6l, iridium oxide-based insoluble anodes 6a to 6l are used, and their upper ends slightly protrude from the liquid surface LL of the plating solution 5 through the electrically insulating frame. Installed. At this time, using a shielding plate (not shown) installed on the anodes 6a to 6l side, the width of the surface of the anodes 6a to 6l facing the plating surface of the polyimide film F1 with a metal thin film (hereinafter referred to as “anode width”). Is adjusted to 85% with respect to the width of the polyimide film F1 with a metal thin film.

  Further, the edge shielding jig is made of electrically insulating plastic, has a height of 1280 mm, a width of 105 mm, a thickness of 4 mm, a distance between opposing inner surfaces of 40 mm, a U-shaped cross section, and a substantially rectangular shape. An edge shielding jig 9 having a shielding plate 10 and a movable plate 11 having a height of 975 mm, a width of 105 mm, and a thickness of 3 mm are pivotally supported on the shielding plate 10 by screws, and the shielding plate 10 is centered on the screws. A throttle shielding plate 9a provided so as to be rotatable in the range of 0 ° to 2 ° was prepared. The movable plate 11 is pivotally supported at a position of 295 mm from the lower end and 90 mm from the horizontal outer end so that the upper end of the movable plate 11 coincides with the upper end of the shielding plate. An oblong slot having a length of 45 mm and a width of 10 mm was provided at a position 25 mm from the upper end and 100 mm from the horizontal outer end.

  In the electroplating cells C1 to C10, the edge shielding jigs 9 were installed at both ends of the polyimide film F1 with a metal thin film that is conveyed so as to be substantially parallel to the anodes 6a to 6j. On the other hand, in the electroplating cells C11 and C12, the throttle shielding plates 9a are installed at both ends of the polyimide film F1 with a metal thin film that is conveyed facing the anodes 6k and 6l substantially in parallel. In each of the edge shielding jig 9 and the throttle shielding plate 9a, the upper end portions of the edge shielding jig 9 and the throttle shielding plate 9a are located 40 mm above the liquid level LL of the plating solution 5, and the upper end portion and the long hole 13 of the throttle shielding plate 9a are formed in the plating solution 5. It was arranged so as to protrude from the liquid level LL, and the fogging amount D was adjusted and installed so that the desired electrodeposition amount and the surface of the copper plating layer 14 of the electrodeposited metalized polyimide film F2 were as smooth as possible. Specifically, in the electrolytic plating cells C1 to C10, the fogging amount D was finely adjusted on the basis of 30 mm so that the plating surface after passing through the electrolytic plating cells C1 to C10 was sufficiently smooth. As a result, the fogging amounts D in the electrolytic plating cells C1 to C10 were all in the range of 27 mm to 33 mm. At the same time, in the electrolytic plating cells C11 and C12, the opening angle α of the movable plate 11 of the throttle shielding plate 9a was set to 2 °, and the maximum fogging amount Dmax was adjusted to 88 mm. In the electroplating cells C11 and C12, considering that the current density in the vicinity of the liquid level LL is suppressed by the movable plate 11, the fogging amount D of the shielding plate 10 was adjusted to 20 mm.

  The film thickness of the copper plating layer obtained by continuous electroplating is 8 μm, the current density for the anodes 6a to 6l in the electroplating cells C1 to C12 is set as shown in Table 1, and the transport speed is adjusted to adjust the copper film thickness as described above. A plating layer was obtained. The plating solution 5 had a sulfuric acid concentration of 100 g / L, a copper sulfate of 180 g / L, and a chlorine concentration of 50 mg / L, and a predetermined amount of an organic additive was added thereto for the purpose of ensuring the smoothness of the copper plating layer. The temperature of the plating solution 5 was set to 27 ° C.

  The film thickness of the copper layer (copper thin film layer + copper plating layer) of the obtained metallized polyimide film F2 was measured with a fluorescent X-ray film thickness meter (manufactured by SII Nanotechnology Inc., model: SFT9250). The measurement is divided into a central part within 80 mm from the longitudinal center line of the metallized polyimide film F2, a left part from 230 mm to 80 mm on the left side from the center line, and a right part from 230 mm to 80 mm on the right side from the center line, The difference between the maximum value and the minimum value at each location was used as an index. In this example, the time required for adjusting the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side was measured, and this was used as an index of the efficiency of the continuous electrolytic plating process. These results are shown in Table 2.

(Example 2)
Except that the edge shielding jig 9 is used for the electrolytic plating cells C1 to C11, the throttle shielding plate 9a is used only for the electrolytic plating cell C12, and the fogging amount D is set as the numerical values in Table 2. In the same manner as in Example 1, a metalized polyimide film F2 was prepared, and it was necessary to adjust the film thickness of the copper layer, and the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side. Time was measured. These results are shown in Table 2.

(Example 3)
Except that the edge shielding jig 9 is used for the electrolytic plating cells C1 to C8, the throttle shielding plate 9a is used for the electrolytic plating cells C9 to C12, and these fogging amounts D are set as the numerical values in Table 2. In the same manner as in Example 1, a metallized polyimide film F2 was prepared, and it was necessary to adjust the film thickness of the copper layer, and the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side. The measured time was measured. These results are shown in Table 2.

Example 4
In the electroplating cells C11 and C12, the opening angle α of the movable plate 11 of the throttle shielding plate 9a is both 0.5 ° and the maximum fogging amount Dmax is adjusted to be 40 mm. Then, the metallized polyimide film F2 was prepared, and the thickness of the copper layer and the time required for adjusting the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side were measured. These results are shown in Table 2.

(Comparative Example 1)
The edge shielding jig 9 is used for the electroplating cells C1 to C12, and the fogging amount D is set so that the plating surface after passing through the electroplating cells C1 to C12 is sufficiently smooth with 30 mm as a reference. Except for the adjustment, a metalized polyimide film F2 was prepared in the same manner as in Example 1, and it was necessary to adjust the film thickness of the copper layer, and the edge shielding jig 9 and the shielding plate on the anodes 6a to 6l side. The measured time was measured. These results are shown in Table 2. In this comparative example, the fogging amounts D in the electroplating cells C1 to C12 were all in the range of 27 mm to 33 mm.

(Comparative Example 2)
In the electroplating cells C11 and C12, the same as in Example 1 except that the opening angle α of the movable plate 11 of the throttle shielding plate 9a is both adjusted to 2.5 ° and the maximum fogging amount Dmax is set to 105 mm. Then, the metallized polyimide film F2 was prepared, and the thickness of the copper layer and the time required for adjusting the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side were measured. These results are shown in Table 2.

(Comparative Example 3)
Among the electroplating cells C1 to C8 having a set current density of less than 3.0 A / dm ² , in the electroplating cells C5 to C8, the fogging amount D of the edge shielding jig 9 is set to a range of 65 mm to 75 mm. A metallized polyimide film F2 was prepared in the same manner as in Example 1 except that the plated surface after passing through C5 to C8 to be electrolytically plated was sufficiently smooth, and the film of the copper layer. The thickness and the time required for adjusting the edge shielding jig 9, the throttle shielding plate 9a, and the shielding plates on the anodes 6a to 6l side were measured. These results are shown in Table 2.

(Comparative Example 4)
In the electrolytic plating cells C11 and C12, the metallized polyimide film F2 was prepared in the same manner as in Comparative Example 1 except that the shielding plate on the anode 6k and 6l side was adjusted so that the smoothness of the plating surface was the best. The thickness of the copper layer and the time required for adjusting the edge shielding jig 9, the throttle shielding plate 9a and the shielding plates on the anodes 6a to 6l side were measured. These results are shown in Table 2. In this comparative example, the anode width of the anodes 6k and 6l was 80% with respect to the width of the polyimide film F1 with a metal thin film.

(Reference example)
A metallized polyimide film F2 was prepared in the same manner as in Comparative Example 1 except that no shielding plate was used on the anodes 6a to 6l side, and required for adjusting the film thickness of the copper layer and the edge shielding jig 9. The measured time was measured. These results are shown in Table 2.

[Evaluation]
From Table 1 and Table 2, in the metallized polyimide film F2 of Examples 1 to 4, the difference between the maximum value and the minimum value of the film thickness is 0.25 μm or less at any position of the left part, the center part, and the right part. It is confirmed that the smoothness of the plated surface is excellent. In Examples 1 to 4, the time required for adjusting the fogging amount was within 70 minutes, and the metallized polyimide film excellent in smoothness of the plating surface could be produced in a relatively short time. It is confirmed.

In contrast, Comparative Example 1 in which only the edge shielding jig 9 is used, Comparative Example 2 in which the opening angle α and the maximum fogging amount Dmax of the throttle shielding plate 9a are out of the present invention, and the set current density is 3.0 A / dm ^2. In Comparative Example 3 in which the amount of fog exceeds 60 mm in a part of the electrolytic plating cell that is less than 1, the smoothness of the plated surface could not be sufficiently improved. Further, in Comparative Example 4 in which the fogging amount of the shielding plate on the anode side was adjusted, the smoothness of the plated surface was relatively good, but this adjustment took 2 hours or more.

DESCRIPTION OF SYMBOLS 1 Continuous electroplating apparatus 2 Unwinding roll 3 Winding roll 4 Plating tank 5 Plating solution 6a-6l Anode 7a-7g Feeding roll 8a-8f Conveyance roll 9 Edge shielding jig 9a Edge shielding jig provided with an inclined part (throttle shielding) Board)
DESCRIPTION OF SYMBOLS 10 Shielding plate 11 Movable plate 12 Support point 13 Long hole 14 Metal (copper) plating layer F1 Resin (polyimide) film with a metal thin film F2 Metallized resin (polyimide) film C1 to C12 Electroplating cell LL Plating liquid level W Plating surface Width D Cover amount Dmax Maximum cover amount Dmin Minimum cover amount α Opening angle

JP 2003-342787 A JP 2011-58057 A JP 2006-316322 A Japanese Patent Laid-Open No. 2004-99950

The present invention comprises a plating tank, a plurality of feed rolls disposed above the plating tank, a plurality of anodes arranged substantially perpendicularly to the plating tank, than the anode of the plurality of in the plating tank A plurality of conveying rolls disposed below, and maintaining a long object to be processed in a substantially horizontal direction through the plurality of power supply rolls and the plurality of conveying rolls, and In the plating solution in the plating tank, the object to be processed is conveyed so as to be substantially parallel to each of the plurality of anodes, and is in contact with the plurality of anodes and a corresponding power supply roll among the plurality of power supply rolls. The present invention relates to a roll-to-roll type continuous electrolytic plating apparatus configured such that a plurality of electrolytic plating cells are configured with a plating surface of an object, and a metal plating layer is sequentially laminated on the plating surface of the object to be processed.

That is, in the present invention, in combination with the edge shielding jig 9, edge shielding is performed in at least one electrolytic plating cell having a set current density of 3.0 A / dm ² or more that affects the plating thickness of the plating surface of the metal plating layer 14. By using the edge shielding jig 9a having an inclined portion instead of the jig 9, the plating surface can be cut off corresponding to the current density distribution in the conveying direction as well as in the width direction. In industrial scale production, a metallized resin film F2 having high smoothness can be easily obtained. Moreover, in the present invention, such a uniform current density is realized mainly by adjusting the fogging amount of the edge shielding jig 9a provided with the inclined portion installed in the electrolytic plating cell having a high set current density. Therefore, the adjustment time can be reduced. In particular, when a later-described throttle shielding plate is employed as the edge shielding jig 9 a having an inclined portion, it is possible to adjust the fogging amount without discharging the plating solution 5 from the plating tank 4. The adjustment time can be greatly reduced.

In addition, it is preferable that the movable plate 11 can be fixed at an arbitrary position through a long hole 13 by a fixing jig (not shown) such as a screw. More preferably, it is provided above the liquid level LL of the liquid 5. By adopting such a configuration, it is possible to adjust the fogging amount D without discharging the plating solution 5 in the plating tank 4 to the outside of the tank , so that the adjustment time can be greatly shortened. .

Claims (12)

A plating layer, a plurality of power supply rolls disposed above the plating layer, a plurality of anodes disposed substantially vertically in the plating layer, and a position below the plurality of anodes in the plating tank. A plurality of transport rolls, and a long object to be processed while maintaining the width direction in a substantially horizontal direction through the plurality of power supply rolls and the plurality of transport rolls, and in the plating tank In the plating solution, the plating surface of the object to be processed is conveyed so as to be substantially parallel to each of the plurality of anodes, and is in contact with the plurality of anodes and the corresponding power supply roll among the plurality of power supply rolls. A plurality of electrolytic plating cells, and a roll-to-roll type continuous electrolytic plating apparatus configured to sequentially laminate a metal plating layer on the plating surface of the workpiece,
The plurality of electrolytic plating cells extend in the conveying direction of the workpiece, the cross section is U-shaped with respect to the extending direction, and surfaces parallel to the extending direction have a substantially rectangular shape, An edge shielding jig that includes a shielding plate that is disposed so as to cover both ends of the object to be processed and shields both ends of the object to be processed from at least a part of each of the plurality of anodes. Provided to be 60 mm, and
Among the plurality of electroplating cells, at least one electroplating cell having a set current density of 3.0 A / dm ² or more is shielded on the surface of the edge shielding jig facing at least the anode. The edge shielding jig provided with an inclined portion configured to be wide at the upper end portion near the liquid surface of the plating solution and narrow at the lower end portion far from the liquid surface is the maximum at the upper end portion of the edge shielding jig. The fogging amount is provided so as to be larger than the fogging amount of the edge shielding jig not provided with the inclined portion and 100 mm or less.
Continuous electrolytic plating equipment.   The continuous electroplating apparatus according to claim 1, wherein the edge shielding jig including the inclined portion is installed in an electroplating cell having at least a set current density.   The continuous electrolytic plating apparatus according to claim 2, wherein the electrolytic plating cell having the highest set current density is the last electrolytic plating cell of the plurality of electrolytic plating cells. The edge shielding jig provided with the inclined portion has a supporting point provided on a side far from the liquid surface of the shielding plate on at least a surface facing the anode among the shielding plate and the substantially rectangular surface of the shielding plate. It is composed of a throttle shielding plate provided with a movable plate attached to the center so as to be rotatable,
The continuous electrolytic plating apparatus according to claim 1, wherein the inclined portion is formed by rotating the movable plate with respect to the shielding plate.   The continuous electrolytic plating apparatus according to claim 4, wherein the movable plate is rotatable with respect to the shielding plate in a range of at least 0 ° to 2 °. The continuous electrolytic plating apparatus according to any one of claims 1 to 5, wherein the long object to be processed is arranged in a substantially horizontal direction through the plurality of power supply rolls and the plurality of transport rolls. And in the plating solution in the plating tank, the plurality of anodes and the corresponding feeding rolls among the plurality of feeding rolls are conveyed so as to be substantially parallel to each of the plurality of anodes. A roll-to-roll type continuous electrolytic plating method in which a plurality of electrolytic plating cells are configured with the plating surface of the object to be processed in contact with the plating surface, and a metal plating layer is sequentially laminated on the plating surface of the object to be processed. ,
The plurality of electrolytic plating cells extend in the conveying direction of the workpiece, the cross section is U-shaped with respect to the extending direction, and surfaces parallel to the extending direction have a substantially rectangular shape, An edge shielding jig provided with a shielding plate that is arranged so as to cover both ends of the object to be processed and shields both ends of the object to be processed from at least a part of each of the plurality of anodes. Installed to be 60 mm, and
Among the plurality of electroplating cells, at least one electroplating cell having a set current density of 3.0 A / dm ² or more is shielded on the surface of the edge shielding jig facing at least the anode. The edge shielding jig provided with an inclined portion configured such that the region to be wide is wide at the upper end portion near the liquid surface of the plating solution and narrow at the lower end portion far from the liquid surface is the maximum at the upper end portion of the edge shielding jig. The fogging amount is set to be larger than the fogging amount of the edge shielding jig not provided with the inclined portion and 100 mm or less.
Continuous electrolytic plating method.   The continuous electrolytic plating method according to claim 6, wherein the edge shielding jig including the inclined portion is installed in an electrolytic plating cell having at least the highest set current density.   The continuous electrolytic plating method according to claim 7, wherein the last electrolytic plating cell among the plurality of electrolytic plating cells is an electrolytic plating cell having the highest set current density.   The continuous electrolytic plating method according to claim 6, wherein the opening angle of the inclined portion is 0.5 ° to 2 °. A base metal film forming step of forming a base metal layer by dry plating without using an adhesive on at least one surface of the insulating resin film, and a copper thin film layer laminated on the base metal layer by dry plating A method for producing a metallized resin film, comprising: a dry plating process for forming a resin film with a thin film; and an electroplating process for laminating a copper plating layer on the resin film with a metal thin film by electrolytic plating,
The manufacturing method of the metallized resin film using the continuous electrolytic plating method in any one of Claims 6-9 which uses this resin film with a metal thin film for the said to-be-processed object for the said electrolytic plating process.   A metal obtained by the method for producing a metallized resin film according to claim 10, wherein a difference between the maximum value and the minimum value of the film thickness distribution in the width direction of the copper plating layer is 0.25 μm or less. Resin film. Stretching in one direction and having a U-shaped cross section with respect to the stretching direction, surfaces parallel to the stretching direction are at least one of a shielding plate having a substantially rectangular shape and a substantially rectangular surface of the shielding plate. And a movable plate attached so as to be rotatable in a range of 0 ° to 2 ° with respect to the shielding plate around the fulcrum, and constitutes a continuous electrolytic plating apparatus, and a set current density is 3.0 A / cm Continuous electroplating apparatus comprising at least one electrolytic plating cell that is ² or more and configured by a throttle shielding plate installed so as to cover both end portions of the workpiece to be conveyed substantially parallel to the anode of the electrolytic plating cell Edge shielding jig for.

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