JP2015124418A - Surface treatment method, and manufacturing method of metalized resin film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metalized resin film having a flat metal conductor layer with little irregularity part.SOLUTION: There is provided a method of performing continuous treatment to a surface of a long film-like member F, which is represented by a metalized polyimide film, having a metal layer at least on one surface while the film is conveyed by a roll-to-roll method. Liquid 53 containing acid is coated on a surface having the metal layer of the film-like member F in a substantially sealed space, and gas containing acid mist is exhausted via an exhaust port provided on a container 51 and outside air is supplied into the container 51 via an air-blowing port provided on the container 51, by which gas in the space is substituted at 15 to 50% per one second.

Description

  The present invention provides a method for surface-treating a film-like member having a metal layer formed on at least one side using an acidic liquid, and a metallized resin film used for a wiring member in an electronic device using the surface-treatment method. On how to do.

  A flexible printed wiring board obtained by patterning a metallized resin film is widely used for wiring members of electronic devices such as liquid crystal panels and mobile phones. As this metallized resin film, a three-layered metallized resin film in which a polyimide film as a resin film and a copper foil are bonded together using an adhesive has been widely used. However, as electronic devices have become lighter, thinner and shorter in recent years, the wiring member wiring is required to have a narrower pitch, and the metalized resin film is required to have a high-quality substrate capable of drawing finer wiring. ing.

  Under such circumstances, a two-layer metallized polyimide film that uses a polyimide film as a resin film and deposits a metal layer without an adhesive layer is drawing attention. Thus, by using a two-layer structure without an adhesive layer, the stable characteristics inherent in polyimide can be fully exerted without being influenced by the characteristics of the adhesive layer, and a higher quality substrate is produced. Because it can. In the following description, the case where polyimide is used for the resin film is referred to as a metallized polyimide film, and when not limited to polyimide, it is simply referred to as a metallized resin film.

  The method for producing a two-layer metallized polyimide film without an adhesive layer as described above includes (1) a casting method in which a polyimide varnish is applied to a copper foil and then heated to form a polyimide film layer, (2) Lamination method in which thermoplastic polyimide adhesive is applied to polyimide film and heat-pressed with copper foil. (3) After a metal layer is directly laminated on the polyimide film surface by sputtering or vapor deposition, electroplating or There is a dry plating method in which a metal layer is thickened using an electrolytic plating method.

  Among these various methods, the dry plating method has an advantage that a two-layer metallized resin film can be continuously produced. For example, a metal seed layer made of nickel, chromium, nickel-chromium alloy or the like is first formed on at least one surface by a dry plating method such as sputtering or vapor deposition while transporting a long resin film by roll-to-roll, and a good material is formed thereon. In order to impart conductivity, a metal film composed of a copper layer is formed. Then, in order to increase the thickness of the conductor layer to be patterned in the subsequent circuit formation, the copper conductive layer is further electroconductive on the metal coating by electroplating alone or by wet plating using a combination of electroplating and electroless plating. It is common to form a body layer.

  The formation of the conductor layer by this electroplating method can also be performed continuously. For example, a long resin film is continuously immersed in a plating solution in a plating tank while being conveyed by roll-to-roll, and the plating solution Continuously electroplating the long resin film by supplying power to the anode and the plating surface on the long resin film while continuously facing the anode (anode) provided inside Can do. In addition, when performing electroplating continuously in this way, generally two or more plating tanks are arranged in parallel along the conveyance direction of a long resin film.

  For example, in Patent Document 1, a metallized resin film having a thickness of 0.5 μm or less is successively immersed in a plating tank arranged in a plurality of rows in which an electrolytic solution is stored so as to face the anode. The method of plating automatically is shown. In the method of Patent Document 1, the energization amount can be controlled for each plating tank, and the energization amount for each plating tank can be uniformly increased by increasing in the subsequent stage with respect to the transport direction of the metallized resin film. It is shown that a good electroplating film can be continuously formed.

  As described above, the two-layer metallized resin film produced by the dry plating method and the electroplating method is subjected to fine wiring processing for a flexible printed wiring board represented by COF (Chip On Film), for example, for a liquid crystal panel. Used for mounting boards. The metallized resin film to be processed in such a fine wiring is particularly required not to have a minute uneven portion on the surface. Roughness of the surface of the resin film, which is a base material, easily affects the smoothness of the surface of the metallized resin film, and when a resin film having irregularities on the surface is used, irregularities are likely to be formed on the surface of the metallized resin film. Therefore, the resin film is required to have no recesses or protrusions with a size in the plane direction of the film of about 20 to 50 μm.

  In addition, in a two-layer metallized resin film, activation of the resin film surface, which is a base material, may be required for good adhesion between the resin film and the metal layer. Therefore, in the production of a metallized resin film, the surface is treated with an acid as a pretreatment prior to electroplating in order to activate the resin film as a base and remove foreign substances. For example, Patent Document 2 discloses that a metal conductor layer with few fine surface defects is removed by applying a surface treatment with an acid to a metalized polyimide film before electroplating to remove foreign matters attached to the surface. The technique to gain is shown. Patent Document 3 discloses a technique for suppressing adverse effects on surface defects of a metal conductor layer after electroplating by defining the surface hardness of a roller that contacts the surface of the film substrate in the surface treatment before electroplating. Has been.

JP 2009-026990 A JP 2013-056777 A JP 2013-181180 A

  As described above, a two-layer metallized resin film having no adhesive layer is required to have no minute unevenness on the metal surface particularly when fine wiring processing is performed as COF. However, when a metallized resin film is produced by continuously treating a long resin film using a dry plating method and an electroplating method, as shown in Patent Document 2, glycolic acid or the like is used as a pretreatment before electroplating. When surface treatment is performed using an acid such as sulfuric acid as the surface treatment liquid, fine irregularities may occur in the metal conductor layer. Moreover, as shown in Patent Document 3, even when the surface hardness of the roller in contact with the film substrate is set to an appropriate range, minute uneven portions may occur in the metal conductor layer.

  The present invention has been made in view of the above-described conventional problems, and uses a surface of a film-like member having a metal layer on at least one surface by using an acid without causing a minute uneven portion that becomes a surface defect in the metal conductor layer. It aims at providing the method of manufacturing the metallized resin film which hardly has a micro unevenness | corrugation part using the method of processing, and its surface treatment method.

  In order to solve the above problems, the present inventor conducted extensive research on a method for producing a metallized polyimide film. As a result, the electroplating is suppressed by suppressing acid mist generated in the surface treatment process as a pretreatment for electroplating. It has been found that it is possible to prevent damage to the metal surface before being applied, and thus it is possible to produce a high-quality metallized polyimide film having no micro unevenness on the surface by electroplating, and the present invention has been completed. .

  That is, the surface treatment method provided by the present invention is a method of continuously treating the surface of a long film-like member having a metal layer on at least one side while conveying it in a roll-to-roll manner, and is almost sealed. In addition, a liquid containing an acid is applied to the surface of the film-like member having the metal layer in the space, and 15 to 50% of the gas existing in the space is replaced per second.

  Further, the electroplating method provided by the present invention is a method of continuously performing electroplating on a surface of a long film-like member having a metal layer on at least one side while transporting it by a roll-to-roll method, The surface treatment method described above is performed. Moreover, the manufacturing method of the metallized resin film provided by the present invention includes the above-described electroplating method after laminating a metal seed layer and a copper coating layer in this order without using an adhesive on at least one side of a long resin film. It is characterized in that the metal conductor layer is formed by increasing the thickness of the copper coating layer.

  Furthermore, the electroplating apparatus provided by the present invention includes an electroplating unit that continuously electroplates a long film-like member conveyed by a roll-to-roll method, and before electroplating in the electroplating unit, An electroplating apparatus comprising a pretreatment unit for continuously surface-treating a long film-shaped member, wherein the pretreatment unit is substantially sealed in which a liquid containing an acid to be applied to the film-like member is stored. And a gas replacement means for replacing 15 to 50% of the gas existing in the space in the container per second.

  According to the present invention, it is possible to obtain a metallized resin film having a flat conductor layer having almost no minute unevenness on the surface. This metallized resin film is particularly suitable for applications such as COF where fine processing is performed.

1 is a schematic side view of an electroplating apparatus to which a surface treatment method of the present invention is preferably applied. It is a schematic side view of the pre-processing part which the electroplating apparatus of FIG. 1 has.

  Hereinafter, an embodiment of a surface treatment method of the present invention will be described with reference to the drawings. In the following description, the surface treatment method according to one embodiment of the present invention is applied to a manufacturing process of a two-layer metallized resin film used for a wiring member in an electronic device, and is particularly one of them. Although applied to the pretreatment process of the electroplating process, the surface treatment method of the present invention is not limited to the application of the electroplating process to the pretreatment process. That is, the surface treatment method of the present invention includes an acid typified by a surface treatment agent while continuously conveying a long film-like member having a metal layer on at least one side typified by a metallized resin film by a roller. The present invention can be widely applied to a method of applying a liquid by dipping or the like to surface-treat a metal surface.

  First, an electroplating apparatus to which the surface treatment method of the present invention is suitably applied will be described with reference to FIG. The electroplating apparatus shown in FIG. 1 is a roll-to-roll method for increasing the thickness of a metallized resin film F having a metal film formed on at least one surface in a dry plating apparatus of the preceding stage (not shown). After the pretreatment is performed on the metallized resin film F transported by the electroplating, electroplating which is wet plating is performed to thicken the metal film formed by dry plating, thereby the metallized resin having a film thickness The film S is produced. In addition, copper is mainly used for the material of the metal film to be thickened by electroplating.

  If it demonstrates concretely, the apparatus shown in this FIG. 1 will be applied to the unwinding roll 11 from which the metallized resin film F wound in roll shape is unwound, and the metal coating of the metallized resin film F conveyed by a roller. The pretreatment part 12 which performs surface treatment, the electroplating part 13 where electroplating is performed to increase the film thickness of the metal film of the metallized resin film F conveyed by the roller, and the metal film is made thicker by electroplating. And a winding roll 14 for winding the metallized resin film S into a roll.

  In the electroplating unit 13, eight parallel anodes (anodes) 22a to 22h are provided in the plating tank 21 in which the plating solution is stored, and a metallized resin film is provided on the anode. Five feeding rolls 23a to 23e above the liquid level and four conveyance guide rolls 24a to 24d inside the plating tank 21 are alternately arranged so that F can continuously face. Then, power is supplied to the anode and the power supply roll by a power supply device (not shown). The inside of the plating tank 21 is divided into four tanks each having two anodes and one conveyance guide roll by a partition plate (not shown).

  The pretreatment part 12 located in the preceding stage of the above-mentioned electroplating part 13 is a part which performs the surface treatment as a pretreatment before the electroplating process on the surface of the metallized resin film F. As shown in FIG. While the metallized resin film F unwound from the roll 11 (not shown in FIG. 2) is conveyed using a plurality of roller pairs 52, 55, 62, 64, the coating device 50, the water washing device 60, the liquid drainer Processing is performed in order in the apparatus 70 and the drying apparatus 80.

  In the coating apparatus 50, the metallized resin film F is continuously immersed in the surface treatment agent 53 by a pair of rollers 52 and 55 provided in the container 51 and a roller 54 positioned below the liquid surface treatment liquid 53. Thus, the surface treating agent 53 is applied to the surface on the metal conductor layer side. The surface treatment of the metallized resin film F is performed by applying the surface treatment agent 53. As a result, a part of the metal surface of the metallized resin film F is melted and roughened, and adheres during the subsequent electroplating. Power is increased. Also, thin rust (oxide film), smut, and foreign matter are removed.

  It is preferable to use an acidic aqueous solution containing an organic solvent for the surface treatment agent 53 used in the coating apparatus 50. For example, it can be prepared by adding an acidic solution and water to an organic solvent such as Arnion (manufactured by Yuken Industry Co., Ltd., trade name: Arnion T-NNO). An inorganic acid is preferably used for the acidic liquid, but sulfuric acid is particularly preferable. What is necessary is just to set the density | concentration of these organic solvents and acidic liquid suitably according to the use of the metallized resin film S. FIG. In addition, the method of performing surface treatment by apply | coating acidic aqueous solution to the metallized resin film F is not limited to an above-described method, You may be based on well-known methods, such as an ultrasonic cleaning method.

  The metallized resin film F surface-treated with the coating device 50 is then sent to the water washing device 60. The water washing apparatus 60 removes the liquid surface treatment agent adhering excessively on the surface of the metallized resin film F by the preceding application apparatus 50 by washing with water, and the water used for washing is preferably pure water. In order to increase the purity, pure water to which an additive is added may be used as necessary. As a method of washing with water, water may be sprayed on both surfaces of the metallized resin film F using a pair of showers 63 arranged above and below the metallized resin film F conveyed in the horizontal direction as shown in FIG. And you may use well-known methods, such as immersing the metallized resin film F in a water tank.

  The metallized resin film F washed with the water washing device 60 is then sent to the liquid draining device 70. The liquid draining device 70 is intended to reduce the load of the subsequent drying device 80 by reducing the amount of water adhering to the metallized resin film F by the front water washing device 60, and the front and back surfaces are moved up and down. Moisture adhering to the metallized resin film F is blown off by blowing compressed air from above and below toward the front and back surfaces of the metallized resin film F conveyed in the horizontal direction. The metallized resin film F dehydrated by the liquid draining device 70 is then sent to the drying device 80. The drying device 80 introduces hot air into the box having the slit-like inlet and outlet of the metallized resin film F conveyed in the horizontal direction and exhausts the gas containing the evaporated water to exhaust the gasified resin film F. Is to be dried.

  By the way, the coating apparatus 50 that performs the surface treatment with the surface treatment agent 53 on the metallized resin film F described above prevents foreign matter from falling into the tank or from adhering to the metallized resin film F. It is housed in a container 51 that is almost sealed with a cover or the like. Therefore, in this container 51, acidic vapor or acidic mist evaporated from the acidic aqueous solution as the surface treating agent 53 exists in a space above the liquid surface of the surface treating agent 53. And the metallized resin film F will be conveyed in this space by several roller pair 52,55. As a result, the metal surface of the metallized resin film F is exposed to an acidic mist drifting in the space, so that the metal surface is inhomogeneously roughened, whereby the metal conductor layer of the copper coating of the metallized resin film F after electroplating. In some cases, fine irregularities were generated on the surface.

  Of course, if no acidic liquid is added to the surface treating agent 53, it is not necessary to consider the adverse effect on the metallized resin film F due to the acidic mist generated in the coating apparatus 50. However, in this case, as described above, it becomes a factor of reducing the ability to remove thin rust (oxide film), smut, and foreign matter by an immersion method using an acid. Therefore, controlling the amount of acidic mist floating in the space is extremely effective for obtaining a high-quality metallized resin film S.

  Therefore, in this coating apparatus 50, the flow of the airflow in the coating apparatus 50 is controlled in order to suppress non-uniform roughness of the metal surface of the metallized resin film F due to the acidic mist drifting in the space atmosphere. Specifically, gas containing acidic mist is exhausted through an exhaust port (not shown) provided in the container 51 of FIG. 2 and outside air is supplied into the container 51 through an air outlet (not shown) provided in the container 51. Thus, the gas existing in the effective space above the liquid surface of the surface treating agent 53 in the container 51 is replaced at a rate of 15 to 50% per second. Thereby, the quantity of the acidic mist which drifts in the container 51 of the coating device 50 can be reduced, and it can prevent that an uneven | corrugated uneven | corrugated | grooved part produces | generates on the metal surface of the metallized resin film F by acidic mist.

  Here, the effective space is substantially a gas phase excluding a portion occupied by equipment such as the conveying means 52 and 55 from a space above the liquid surface of the surface treatment agent 53 in the substantially sealed container 51. It is a space that can be obtained. Also, the term “closed” means that the long film-like metallized resin film F that is continuously transported into and out of the container 51 includes a slit-shaped inlet and outlet, and the container 51 described above. This means that the container 51 is hermetically sealed with a cover or the like except for an exhaust port and a blower port for gas replacement.

  When the above gas replacement amount exceeds 50% per second, not only the acid mist but also necessary water is exhausted from the container 51, so that the humidity of the effective space in the container 51 is excessively lowered, and the wet environment is not lost. The water film formed on the outer peripheral surface of the roller that plays the role of transporting the metallized resin film F becomes insufficient, and there is a risk that scratches due to rubbing of the roller may occur. Further, in this case, there is a possibility that the water washing ability of the subsequent water washing device 60 may be reduced. On the other hand, when the gas replacement amount is less than 15% per second, the amount of the acidic mist staying is excessive, and the metal surface of the metallized resin film F is liable to be unevenly roughened.

  It should be noted that the amount of acidic mist present in the container 51 of the coating device 50 is not limited to replacing the gas in the container 51 described above, and the liquid temperature of the surface treatment agent 53 stored in the container 51 and the amount of acid mist in the container 51. Since it is affected to some extent by the flow rate, the transport speed of the metallized resin film F, the number of rollers for transporting the metallized resin film F, etc., in addition to the replacement of the gas in the container 51 described above, adjust these appropriately. Thus, the adverse effect of the metallized resin film F on the metal surface can be more effectively prevented.

  As a method of controlling the amount of gas replacement in the container 51 described above, an air conditioner, a fan, or the like is installed in the space so that an air flow having a desired flow velocity is formed between the air blowing port and the exhaust port. The flow rate may be adjusted, or the flow rate may be adjusted by installing a suction fan or a blower fan outside the exhaust port or outside the blower port. Further, instead of adjusting the flow rate of these devices, or in parallel with this, the opening degree of the air blowing port or the exhaust port may be adjusted. In addition, these ventilation openings, exhaust openings, and gas blowing means such as air conditioners and fans are collectively referred to as gas replacement means.

  In order to control the amount of acidic mist in the container 51 of the coating apparatus 50, the container 51 is opened to the atmosphere without being almost sealed as described above, or the entire pretreatment unit 12 shown in FIG. You may control the airflow in the room | chamber interior in which the whole plating apparatus to show is installed. In this case, for example, an air outlet and an exhaust port are installed in a room in which the entire plating apparatus in FIG. 1 or the entire pretreatment unit 12 in FIG. 2 is provided.

  However, for example, when the indoor gas is sucked by an exhaust fan provided in a duct connected to the exhaust port, the atmosphere around the exhaust port becomes negative pressure and the indoor atmosphere is attracted. There is a risk of spreading unnecessarily. In order to prevent this, it is more preferable to install the exhaust port in the vicinity of the coating device 50. For example, the exhaust port is preferably provided on the side wall of the treatment tank. Moreover, it is preferable to install an air outlet and an exhaust port so that the flow of an airflow reverses in the conveyance direction of the metallized resin film F.

  Next, a case where a two-layer metallized resin film is manufactured by forming a metal layer on at least one side of a long resin film without using an adhesive by electroplating including the surface treatment method described above will be described. First, polyimide film, polyamide film, polyester film such as polyethylene terephthalate (PET) or polyethylene terephthalate (PEN), polytetrafluoroethylene film, polyphenylene sulfide film, polyethylene naphthalate film, or liquid crystal polymer film A long resin film having a thickness of about 10 to 50 μm, such as a film, is prepared. The specific material of the long resin film is appropriately selected in consideration of heat resistance, dielectric properties, electrical insulation, chemical resistance in the manufacturing process of the printed wiring board and subsequent processes, usage, and the like. The specific thickness is also appropriately selected according to the application.

  A metal seed layer made of nickel, chromium, or the like is formed on at least one surface of the long resin film by a dry plating method using a vapor deposition method or a sputtering method. This metal seed layer plays a role of improving the adhesion between the long resin film and the metal conductor layer and the insulation reliability of the flexible printed wiring board. It is preferable to use nickel or a nickel alloy as such a metal seed layer. In the case of a nickel alloy, it can be obtained by adding one or more elements selected from chromium, vanadium, titanium, molybdenum, cobalt, and tungsten to nickel. Among these, a nickel-chromium alloy is preferable. The chromium content is more preferably 15 to 25% by mass. This is because such a nickel-chromium alloy has high insulation reliability and can easily form a wiring pattern.

  The thickness of the metal seed layer is appropriately selected from the type and composition of the metal or alloy forming the metal seed layer, the workability of the wiring on the flexible printed wiring board, the adhesion required for the wiring, and the insulation reliability. However, generally 3-50 nm is preferable. If the thickness of the metal seed layer is less than 3 nm, the etching solution is used to remove the metal layer (metal conductor layer and metal seed layer) other than the wiring portion by flash etching or the like to form a wiring pattern. There is a possibility that a problem may occur in which the wiring floats up. On the other hand, if the thickness of the metal seed layer exceeds 50 nm, when the wiring pattern is finally formed by flash etching or the like, the metal layer may not be completely removed and may cause an insulation failure between the wirings. is there.

  A metal film is formed by laminating copper or the like on the metal seed layer. The thickness of the copper layer to be laminated here is preferably 0.01 to 1 μm, and particularly preferably 0.1 to 0.5 μm. If the thickness of the copper layer is less than 0.01 μm, a problem may easily occur in the electrical conductivity of the wiring portion on the flexible printed wiring board, or a problem in strength may occur. On the other hand, the film formation rate by the dry plating method is slower than the film formation rate by the electroplating method. Therefore, if the film formation exceeds 1 μm by the dry plating method, the productivity is lowered.

  Thereafter, the copper layer that is the metal conductor layer is thickened by using the above-described electroplating method or electroless plating method, or a method in which both are combined. The film thickness in the case of thickening the copper layer, which is a metal conductor layer, by electroplating or electroless plating, or a combination of both, is subtractive or semi-conductive in wiring patterning of flexible printed wiring boards. It depends on which of the additive methods is selected. That is, the thickness of the copper layer is preferably 5 to 12 μm when the wiring is formed by the subtractive method, and 0.5 to 4 μm when the wiring is formed by the semi-additive method. In addition, the electroplating method is not specifically limited, For example, a well-known electroplating method can be used in copper sulfate aqueous solution.

  The surface treatment method of the present invention has been described on the assumption that it is applied to a metallized resin film used for a wiring member in an electronic device. However, the film-like member targeted by the surface treatment method of the present invention is this. It is not limited to this, and any film-like member having a metal layer on at least one surface that is surface-treated with a liquid treating agent while being conveyed using a roller can be suitably applied.

  Such a film-like member having a metal layer on at least one side is not only the above-mentioned two-layer metallized resin film, but also a general metallized resin film or metal used other than the above-described wiring member in an electronic device. Examples thereof include thin glass and plastic laminated on each other, a metal thin plate having a thickness of 0.3 mm or less, and foil. Further, the liquid treatment agent is not limited to a surface treatment agent composed of a solvent mainly composed of water and a solute, and may be various surface treatment agents containing an acid. If these surface treatment agents are surface treatment agents containing a strong acid, more remarkable effects can be obtained.

  Further, the metallized resin film treated by the surface treatment method of the above-described embodiment of the present invention is obtained by electroplating a metallized resin film having a metal film laminated on at least one side of a long resin film by a dry plating method. However, the method for producing a metallized resin film (when using a polyimide film for a long resin film) is not limited to this method. Absent.

  Hereinafter, the surface treatment method of the present invention will be described in more detail using examples and comparative examples. In addition, the determination of the presence or absence of minute uneven portions in the following examples and comparative examples is inspected over the entire length of the metallized resin film, and a recess or protrusion having a size in the surface direction of the film of 20 to 50 μm is present. If there was, it was judged that there was a minute uneven part.

Example 1
Using a continuous electroplating apparatus as shown in FIG. 1, a long metallized resin film F wound in a roll shape is unwound from an unwinding roll 11 and continuously conveyed by a roller, the pretreatment unit 12. After the surface treatment was performed on the metal coating of the metallized resin film F, the copper layer was thickened by plating with the electroplating unit 13, and the resulting metallized resin film S was wound up by the winding roll 14. .

  For the metallized resin film F to be unwound from the unwinding roll 11, nickel-20 having a film thickness of 10 nm is formed in advance on the surface of a 38 μm-thick polyimide film (trade name Kapton (registered trademark), manufactured by Toray DuPont Co., Ltd.). A mass% chromium alloy film was formed, and a copper layer having a thickness of 100 nm was laminated on the surface of the alloy film.

  In the electroplating section 13, a plating solution containing 100 g / L of sulfuric acid and 180 g / L of copper sulfate and having a chlorine content of 50 mass ppm is used, and additives are added to ensure smoothness of the copper plating film. did. The copper layer of the metallized resin film F was thickened to 8 μm by introducing the metallized resin film F into the electroplating portion 13 at a conveyance speed of 3 m / min. As a pretreatment of the electroplating in the electroplating unit 13, a pretreatment was performed in the pretreatment unit 12 including the coating device 50, the water washing device 60, the liquid draining device 70, and the drying device 80 shown in FIG. As the surface treating agent 53 of the coating apparatus 50, an aqueous solution in which alanion was adjusted to 4.7 ml / L and sulfuric acid was adjusted to 25 g / L was used. Pure water was used as the cleaning liquid of the water washing device 60.

  A side surface of the container 51 of the coating apparatus 50 was provided with one air outlet and one air outlet, and a variable flow rate air blowing fan was installed at the air outlet. The flow rate of the blower fan was adjusted to replace 23% of the gas containing acidic mist in the space of the container 51 per second. In this way, the metallized resin film S was produced by performing electroplating after surface treatment. As a result of inspecting the presence or absence of minute uneven portions on the surface of the metallized resin film wound up in the form of a roll on the winding roll 14, no minute uneven portions are generated even when 500 rolls are inspected, and the high quality The two-layer metallized resin film could be produced.

(Example 2)
In the container 51 of the coating device 50, a large number of openings are provided on both side surfaces facing each other in the transport direction of the metallized resin film F. Then, the flow rate of the variable flow rate blower fan was adjusted to replace 29% of the gas containing acidic mist in the space of the container 51 per second. In addition, this ventilation fan was provided in the opening part located in the downstream with respect to the conveyance direction of the metallized resin film F, and airflow was sent so that the direction in which the metallized resin film F was conveyed may be opposed.

  A metallized resin film S was produced in the same manner as in Example 1 except for the above. As a result of inspecting the presence or absence of minute uneven portions on the surface of the metallized resin film wound up in the form of a roll on the winding roll 14, no minute uneven portions are generated even when 500 rolls are inspected, and the high quality The two-layer metallized resin film could be produced.

(Comparative Example 1)
A metallized resin film S was produced in the same manner as in Example 1 except that the flow rate of the variable flow rate blowing fan was adjusted to replace 5% of the gas containing acidic mist in the space of the container 51 per second. As a result of inspecting the surface of the metallized resin film wound up in the form of a roll on the take-up roll 14 for the presence of minute irregularities, the minute irregularities were found before 500 rolls were inspected.

(Comparative Example 2)
A metallized resin film S was produced in the same manner as in Example 1 except that the flow rate of the variable flow rate blowing fan was adjusted to replace 56% of the gas containing acidic mist in the space of the container 51 per second. As a result of inspecting the surface of the metallized resin film wound up in the form of a roll on the take-up roll 14 for the presence of minute irregularities, the minute irregularities were found before 500 rolls were inspected.

DESCRIPTION OF SYMBOLS 11 Unwinding roll 12 Pre-processing part 13 Electroplating part 14 Winding roll 50 Coating apparatus 60 Water washing apparatus 70 Liquid draining apparatus 80 Drying apparatus

Claims (6)

A method of continuously treating the surface of a long film-like member having a metal layer on at least one side while transporting it in a roll-to-roll manner,
A liquid containing an acid is applied to the surface of the film-like member having the metal layer in a substantially sealed space, and 15 to 50% of the gas existing in the space is replaced per second. Surface treatment method.   The film-like member is washed with water after the application, the water adhering to the film-like member is drained by the water washing, and moisture that cannot be removed by the draining is dried. The surface treatment method as described.   3. A surface treatment method according to claim 1 or 2, wherein a long film-like member having a metal layer on at least one surface is continuously electroplated on the surface while being conveyed by a roll-to-roll method, and the surface treatment method according to claim 1 or 2 as pretreatment The electroplating method characterized by performing.   The electroplating method according to claim 3, wherein the electroplating forms a copper layer, and the acid is sulfuric acid.   After laminating a metal seed layer and a copper coating layer in this order without using an adhesive on at least one surface of the long resin film, the copper coating layer is made thicker by using the electroplating method according to claim 3 or 4. Forming a metal conductor layer. A method for producing a metallized resin film.   An electroplating unit that continuously electroplates a long film-like member conveyed by a roll-to-roll method, and a surface treatment is continuously applied to the long film-like member before electroplating by the electroplating unit. An electroplating apparatus comprising a pretreatment unit for applying, wherein the pretreatment unit includes a substantially sealed container storing a liquid containing an acid to be applied to the film-like member by dipping, and a container in the container per second. An electroplating apparatus comprising gas replacement means for replacing 15 to 50% of the gas present in the space.

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