JP2010053447A - Method and device for forming film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a film, with which malfunction of sticking of a surface of a first metal film and that of a second metal film to each other, and malfunction of occurrence of a wrinkle etc. are prevented without lowering production efficiency of a double-sided laminated substrate. <P>SOLUTION: In the method for film forming of the double-sided laminated substrate, metal films are film formed on both faces of an organic resin film F roll-to-roll conveyed in an atmosphere of reduced pressure, wherein a first metal film is film formed on one surface of the organic resin film F via film forming means 13a, 13b using a dry-type plating method, an oxide film is formed on a surface of the first metal film via a dry-type surface treating means 11, and subsequently a second metal film is film formed on the other surface of the organic resin film F via the film forming means 13a, 13b using the dry-type plating method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a film forming method and a film forming apparatus for forming metal films on both surfaces of an organic resin film under a reduced pressure atmosphere.

  Since organic resin films are flexible and easy to process, those with a metal film or oxide film formed on the surface are widely used in the industry as electronic parts, optical parts, packaging materials, etc. . In an electronic component, a flexible printed circuit board in which wiring is formed with a metal film on the surface of an organic resin film is frequently used, and for example, it is adopted as a substrate connected to a liquid crystal display. In recent years, with the progress of miniaturization of liquid crystal display pixels, high-precision patterns have become essential for such flexible printed circuit boards, and at the same time, there are more highly reliable boards that do not have electrical problems even if the patterns are narrowed. It is requested.

  In the production of such a flexible printed circuit board, a metal substrate is laminated on an organic resin film to produce a laminated substrate, and a wiring pattern is formed on the laminated substrate by a so-called subtractive method or semi-additive method. Has been done since. In either method, a photoresist pattern is printed, exposed, and developed on the surface of the metal film, or a dry film resist is laminated, exposed, and developed to form a wiring pattern. However, the subtractive method is covered with a resist. This is a method of manufacturing a printed circuit board by removing an unremoved metal film by etching. On the other hand, the semi-additive method is a film as a wiring by further attaching a metal film to the surface of a metal film at a location not covered with a resist. In this method, after securing the thickness, an unnecessary metal film is removed to manufacture a printed circuit board.

  By the way, in the laminated substrate of the flexible printed circuit board, until now, the single area layer substrate in which the metal film is formed only on one side of the organic resin film has been the center, but with the demand for smaller and faster electronic circuits. An attempt has been made to use a double-sided laminated substrate in which metal films are formed on both sides of an organic resin film. In such a double-sided laminated substrate, one surface can be used as a circuit, and the other surface can be used for heat dissipation, or both surfaces can be used as a circuit. Furthermore, an attempt has been made to realize a double-sided laminated substrate provided with a multilayer circuit formed by laminating a plurality of metal films on one side or both sides in an organic resin film.

  As a method for efficiently producing such a double-sided laminated substrate, for example, as shown in Patent Document 1, a method of continuously producing a double-sided laminated substrate while conveying an organic resin film by roll-to-roll is disclosed. Has been. However, in this method, since a metal foil is attached to the organic resin film by thermocompression bonding, it has been difficult to achieve both the above-described narrow pitch of the flexible printed board and high reliability.

  Therefore, instead of thermocompression bonding of metal foil, a double-sided laminated substrate can be efficiently produced by forming a metal film on an organic resin film conveyed by roll-to-roll using a so-called metalizing method. Can be considered. Here, a method of forming a metal film on the surface of a nonmetallic substrate by a dry plating method such as a physical film forming method or a chemical film forming method is referred to as a metalizing method. In recent years, the metallizing method has been widely used from decorative items to electronic device parts such as flexible printed boards, and is expected as a technology capable of achieving both a narrow pitch and high reliability.

  Such a technique for forming a metal film on one side of an organic resin film using a metalizing method has been conventionally known. For example, Patent Document 2 discloses that one side of a film using a vacuum deposition method or a sputtering method. A technique for producing a two-layer laminated substrate comprising two layers of a film layer and a coating layer by forming a coating material on the substrate is disclosed.

  In order to cope with narrow pitch while ensuring high reliability, a base metal layer such as nickel or chromium is provided on the surface of an organic resin film such as a polyimide film by a dry plating method such as sputtering or vapor deposition. A copper thin film layer is provided on the layer by a dry plating method to produce a thin film laminated substrate. Further, by applying electrolytic copper plating to the surface of the copper thin film layer, high adhesive strength is obtained without using an adhesive or thermocompression bonding. A method of manufacturing a two-layer laminated substrate having a material has been used.

Japanese Patent No. 3675805 Japanese Patent Laid-Open No. 62-247073

  However, when the film is formed on both sides by the metalizing method on the organic resin film conveyed by roll-to-roll, the reduced pressure atmosphere can be used regardless of the physical film forming method or the chemical film forming method. Since the organic resin film is taken up by the take-up roll immediately after the film is formed below, after forming the first metal film on one surface, the second metal film is formed on the other surface. When the winding is performed, the metal films come into contact with each other. At this time, if the winding pressure is high, the metal film has small protrusions, or the surface temperature of the metal film is high, the surface of the newly formed metal film and the previously formed metal surface In some cases, the surface of the glass sticks to the surface.

  In addition, when the second metal film is formed, the surface of the first metal film is in direct contact with the metal surface of the cooling can roll. As compared with this, there was a problem that slipping was worse and wrinkles were likely to occur in the organic resin film. That is, in the metalizing method, since the temperature of the organic resin film rises, the organic resin film is wrinkled unless the organic resin film stretched accordingly can be appropriately slid on the surface of the cooling can roll. It has occurred.

  These problems are particularly remarkable when a metal film of copper or copper alloy, which is a soft metal having a relatively low melting point and is easy to grow crystals, is formed. Therefore, the tension at the time of winding is controlled in a very low range, the rise in temperature at the time of film formation is suppressed, or the interleaf is made up of the first metal film and the second metal film when winding the organic resin film. In order to prevent the metal films from coming into contact with each other, measures have been taken.

  However, these measures require problems such as winding misalignment in the organic resin film wound up in a roll shape and a decrease in production efficiency, and a new mechanism for using slip sheets. There was a new problem of complication. In addition, although the slip sheet can be used several times, there are operational problems such as cost increase and quality control of the slip sheet.

  In view of the above-described conventional circumstances, the present invention reduces the production efficiency of a double-sided laminated substrate even if a metal film is formed on both sides of an organic resin film conveyed by roll-to-roll using a metalizing method. It is an object of the present invention to propose a film forming method that can prevent a problem that the surface of the first metal film and the surface of the second metal film stick together, a problem that wrinkles occur, and the like.

  In order to achieve the above object, the film forming method provided by the present invention is a method for forming a double-sided laminated substrate in which a metal film is formed on both sides of an organic resin film conveyed by a roll-to-roll under a reduced pressure atmosphere. Then, after forming a first metal film on one surface of the organic resin film by a dry plating method and forming an oxide film on the surface of the first metal film by a dry surface treatment, the organic resin film A second metal film is formed on the other surface by dry plating.

  Further, the film forming apparatus provided by the present invention is a roll equipped with a film forming means for forming a metal film by dry plating on one side of an organic resin film conveyed by a roll-to-roll under a reduced pressure atmosphere. A two-roll film forming apparatus, a dry surface treatment for forming an oxide film on the surface of the metal film at a position along the transport path of the organic resin film and behind the film forming means in the transport direction It is characterized by having means.

  According to the present invention, it is possible to manufacture a double-sided laminated substrate that is free from defects such as sticking of metal films and generation of wrinkles without lowering the production efficiency, so a narrow pitch is ensured while ensuring high reliability. It is possible to provide a flexible printed circuit board corresponding to the above.

It is a conceptual diagram of the roll-to-roll film-forming apparatus for implement | achieving one specific example of the film-forming method of this invention. It is a modification of the roll-to-roll film-forming apparatus of FIG. It is a conceptual diagram of the roll-to-roll film-forming apparatus for implement | achieving the other specific example of the film-forming method of this invention.

  In the film forming method of the present invention, a first metal film is formed on one surface of an organic resin film conveyed by a roll-to-roll under a reduced-pressure atmosphere by a dry plating method. An oxide film is formed on the surface by dry surface treatment, and then a second metal film is formed on the other surface of the organic resin film by a dry plating method.

  Since the surface of the first metal film can be inactivated by forming an oxide film on the surface of the first metal film, the winding pressure is high when forming the second metal film. Even if there is a situation where the metal film has small protrusions or the surface temperature of the metal film is high, avoiding problems such as wrinkles and sticking of metal films without considering them at all Can do. Thereby, a smooth metal film can be formed on both surfaces of the organic resin film conveyed by roll-to-roll.

  Next, a specific example of the film forming method according to the present invention will be described with reference to FIG. FIG. 1 is a schematic view of a roll-to-roll film forming apparatus for realizing a specific example of such a film forming method as viewed from the front.

The roll-to-roll film forming apparatus shown in FIG. 1 includes a rectangular parallelepiped vacuum vessel 1 that accommodates most of its components. If this vacuum vessel 1 can hold | maintain the state pressure-reduced in the range of 10 < ^-4 > Pa-1Pa, the shape will not be ask | required and a cylindrical shape may be sufficient. The inside of the vacuum container 1 is divided into three zones including an unwinding chamber 2, a film forming chamber 3, and a winding chamber 4. These three zones are isolated from each other by the cooling can roll 12 and the partition wall 5, and can be pressure-controlled by independent evacuation systems (not shown).

  In the unwinding chamber 2, there are an unwinding roll 6 for unwinding the organic resin film F wound in a roll shape, and a pre-deposition dry surface treatment means 10 for dry-treating the surface of the organic resin film F before film formation. Is provided. In the film forming chamber 3, film forming means 13 a and 13 b are provided at positions facing the cooling can roll 12. The winding chamber 4 is provided with a winding roll 9 and post-deposition dry surface treatment means 11 for forming an oxide film on the surface of the metal film.

  In addition, an unwinding side guide roll 7 a and an unwinding side tension roll 8 a are provided on the transport path from the unwinding roll 6 to the cooling can roll 12, and the unwinding roll 9 extends from the cooling can roll 12. A winding side tension roll 8b and a winding side guide roll 7b are provided in the transport path. A coolant supplied from the outside of the vacuum vessel 1 circulates inside the cooling can roll 12.

  The organic resin film F is unwound from the unwinding roll 6 by the roll-to-roll film forming apparatus having the above-described structure, guided by the unwinding side guide roll 7a, and one-side surface by the dry surface treatment means 10 before film formation Then, the tension is controlled by the unwinding side tension roll 8a, and the sheet is conveyed while contacting along the outer peripheral surface of the cooling can roll 12. While the organic resin film F is in contact with the surface of the cooling can roll 12, the first metal film is formed by the film forming means 13a and 13b on the surface opposite to the contact region. . At this time, since the organic resin film F is cooled by the cooling can roll 12, temperature damage due to a film forming process such as sputtering can be suppressed. The organic resin film F on which the first metal film has been formed passes through the take-up side tension roll 8b, and after the film formation, the dry surface treatment means 11 forms an oxide film (copper oxide film) on the surface of the first metal film. ) Is formed. Then, it winds up by the winding roll 9 through the winding side guide roll 7b.

  With the above operation, a single area layer substrate in which the first metal film is formed on one surface of the organic resin film F is obtained. Next, the single area layer substrate wound in a roll shape is removed from the winding roll 9 of the roll-to-roll film forming apparatus, and the second surface is not formed on the other surface where the first metal film is not formed. It is set on the unwinding roll 6 of the roll-to-roll film forming apparatus so that a metal film can be formed. Thereafter, the second metal film is formed by operating in the same manner as described above, and a double-sided laminated substrate wound in a roll shape can be obtained. Since it is not necessary to form an oxide film on the surface of the second metal film, the start of the dry surface treatment means 11 is stopped after the film formation when the second metal film is formed.

  The oxide film formed by the above method is removed before entering the next step. For example, when performing electrolytic copper plating on both surfaces of the organic resin film F in the next step, the oxide film is removed before the electrolytic copper plating treatment. The removal of the oxide film is preferably performed using dilute dilute sulfuric acid or sodium persulfate of about 1 to 5%. In addition, when performing electrolytic copper plating in the next process, since the copper plating bath is sulfuric acid acid, it is not necessary to perform the water washing process after oxide film removal.

  Next, the film forming means 13a and 13b and the post-deposition dry surface treatment means 11 will be described in more detail. The film forming means 13a and 13b are for forming a metal film on one surface of the organic resin film F by a metalizing method using a dry plating method. As a film forming method by the metalizing method, there are a physical film forming method such as a vacuum deposition method and a sputtering method, and a chemical film forming method such as a chemical vapor deposition method (CVD). More specifically, the vacuum deposition method is a method of forming a thin film on a substrate by heating and evaporating a film forming material of an evaporation source by resistance heating or electron gun irradiation. A plasma-assisted vapor deposition method is also known in which plasma is formed between an evaporation source and a substrate for the purpose of adhesion and densification of a thin film during vapor deposition.

  In addition, the sputtering method uses a target obtained by forming a film forming material into a plate shape, generates plasma between the substrate and the target using the plasma generation method using the target as a discharge electrode, and uses a potential gradient. In this method, a target material is knocked out by irradiating and colliding ions with a target surface to form a thin film of the target material on a substrate. On the other hand, in chemical vapor deposition (CVD), a thin film is formed on a substrate by vaporizing and introducing inorganic or organic or a mixture thereof as a raw material gas in the vicinity of the substrate and causing a chemical reaction using heating or plasma. It is a method of forming. When plasma is used, an apparatus configuration similar to sputtering can be used.

  In any of the above film forming means, it has been confirmed that the use of plasma during film formation has an effect on adhesion and densification of the thin film. That is, by using plasma during thin film formation, the gas barrier film improves the gas barrier property, the antireflection film improves the optical characteristics, and the thin metal laminated substrate adheres between the underlying metal layer and the organic resin film. Will improve.

  The plasma is formed by installing a discharge electrode in the film formation chamber 3 and applying a DC or AC voltage thereto, or irradiating microwaves at an arbitrary place using a waveguide. Can be formed.

  The material and thickness of the metal film formed by the film forming means 13a and 13b can be appropriately determined according to the application. For example, in the case of producing a two-layer laminated substrate by performing electrolytic copper plating on the surface of the base metal layer, the copper thin film layer provided on the base metal layer, and the copper thin film layer, nickel Alternatively, a known metal can be used as the two-layer laminated substrate such as nickel alloy, chromium, or chromium alloy. In FIG. 1, a sputtering cathode having a nickel chromium alloy sputtering target for forming a base metal layer is formed on the film forming means 13a, and a sputtering cathode having a copper sputtering target for forming a copper thin film layer on the film forming means 13b. An example of when.

  The film thickness of the base metal layer is preferably 7 nm to 50 nm, and the film thickness of the copper thin film layer is preferably 50 nm to 500 nm. Further, electrolytic copper plating is performed to form a two-layer laminated substrate having a copper film thickness of 6 μm or more. If a copper thin film layer having a film thickness of 6 μm can be formed by a dry plating method, electrolytic copper plating is not necessary. The film thicknesses of the base metal layer and the copper thin film layer can be determined by appropriately adjusting the conveyance speed of the organic resin film F and the input power to the sputtering cathode. In the present invention, metal layers such as a base metal layer and a copper thin film layer formed by the film forming means 13a and 13b using a dry plating method are collectively referred to as a metal film.

  The post-deposition dry surface treatment means 11 performs dry surface treatment on the surface of the metal film formed by the film formation means 13a and 13b to form an oxide film. By this dry surface treatment, the activity of a fresh metal thin film after film formation can be suppressed.

  That is, when the organic resin film F is wound up without forming an oxide film after forming the first metal film, the metal of the cooling can roll 12 is formed when forming the second metal film. Since the first metal film is in direct contact with the surface to be manufactured, defects such as wrinkles are likely to occur in the organic resin film F due to the surface activity of the first metal film in a fresh state. Further, when the second metal film is formed and wound around the take-up roll 9 in a roll shape, the first and second metal films formed on the front and back surfaces of the organic resin film F are in contact with each other. Will do. At this time, if the winding pressure is high, the metal film has small protrusions, or the surface temperature of the metal film is high, the surface activity of the first metal film in the fresh state is described above. The first and second metal films stick to each other.

  When such sticking between the first and second metal films occurs, the film is damaged. Although it cannot be confirmed by visual observation, if a pinhole due to the adhesion between the first and second metal films occurs, a pinhole or the like in the two-layer laminated substrate obtained by subjecting the copper thin film layer to electrolytic copper plating in the next step May result in a decrease in yield and quality problems.

  On the other hand, when the first metal film surface is subjected to an oxidation treatment, which is a dry surface treatment after film formation, an oxide film is formed and the first metal film surface may be in an inactive state. it can. This eliminates sticking between the first and second metal films, and the cooling can roll 12 and the organic resin film F come into contact with each other through the oxide film. Thus, the organic resin film F becomes slippery on the cooling can roll 12, and the generation of wrinkles of the organic resin film F is avoided.

  Specific methods of post-deposition dry surface treatment for surface oxidation of the first metal film include a plasma treatment method using plasma and a method of irradiating the organic resin film F with an ion beam using an ion source. However, it is more preferable to use an ion source. In the case of plasma treatment, the treatment atmosphere is mainly oxygen gas, and the space area in which the plasma exists is widened. Therefore, oxygen to the adjacent film formation chamber 3 that needs to block oxygen as much as possible is used. This is because it is necessary to provide a differential exhaust facility and the like to prevent the outflow of the air and to sufficiently shield it, and the apparatus becomes complicated.

  On the other hand, when using an ion source, a plasma discharge is generated in a magnetic field gap to which a strong magnetic field is applied, and cations in the plasma are irradiated as an ion beam by electrolysis with an anode. It can be limited, and the spatial spread of oxygen or the like can be reduced as compared with the plasma treatment. Therefore, it is possible to simplify the shielding of oxygen to the adjacent film formation chamber 3. FIG. 1 shows an example in which an ion source is employed as the dry surface treatment means 11 after film formation.

  The conditions for using the ion source are as follows: the atmospheric pressure of the winding chamber 4 is 0.1 Pa to 0.2 Pa, oxygen, water vapor, carbon dioxide, or carbon monoxide is contained 50% to 100% (the rest is argon gas), A voltage of 0.5 KV may be applied to the ion source. Thus, it is preferable that the atmosphere of the dry surface treatment after film formation contains any one selected from oxygen, water vapor, carbon dioxide, or carbon monoxide. This is because oxygen, water vapor, carbon dioxide, or carbon monoxide serves as an oxygen source and can form an oxide on the surface of the metal thin film.

  When performing dry surface treatment by plasma treatment after film formation, an electrode for plasma treatment is installed instead of an ion source, a potential of 1 KV to 3 KV is applied to the electrode, and an atmospheric pressure is set to 0.1 Pa to 0.2 Pa. The atmosphere may contain 50% to 100% of oxygen, water vapor, carbon dioxide, or carbon monoxide (the remainder is argon gas). An example in which such plasma processing is performed is shown in FIG. In FIG. 2, in addition to using the plasma processing apparatuses 110 and 111 as the dry surface treatment means before film formation and the dry surface treatment means after film formation, the film formation chamber 3 and the unwinding chamber 2 are used. It differs from FIG. 1 that it is arrange | positioned between the winding chambers 4, and these are isolated by the partition 5 and the unwinding side and winding side auxiliary | assistant guide rolls 14a and 14b.

  The thickness of the oxide film formed by these dry surface treatment means 11 and 111 after film formation is preferably 2 nm to 1/2 the film thickness of the first metal film. When the film thickness of the oxide film is larger than ½ of the film thickness of the first metal film, the next step performed after the double-sided laminated substrate is manufactured, for example, the wiring pattern by the subtractive method or the semi-additive method described above In the pretreatment of the forming process or other electrolytic copper plating process, the thickness of the oxide film to be removed becomes thick, which is economically disadvantageous. On the other hand, when the thickness of the oxide film is less than 2 nm, the oxide film is incomplete and sticking occurs. When considering the effect of economy and sticking prevention, the thickness of the oxide film is more preferably 2 nm to 10 nm.

  The dry surface treatment may be performed on the organic resin film before forming the metal film. That is, as shown in FIGS. 1 and 2, the pre-deposition dry surface treatment means 10 and 110 may perform pre-deposition dry surface treatment using a plasma processing apparatus or an ion source. By performing these treatments, the surface of the organic resin film is modified and adhesion is improved. Specific processing conditions for the dry surface treatment before film formation may be appropriately determined according to the purpose. Further, the dry surface treatment before film formation and the dry surface treatment after film formation may be different types of dry surface treatment.

  Next, another specific example of the film forming method according to the present invention will be described with reference to FIG. FIG. 3 is a schematic view of a roll-to-roll film forming apparatus for realizing another specific example of the film forming method as viewed from the front.

  In the roll-to-roll film forming apparatus shown in FIG. 3, most of the components are housed in the vacuum vessel 201, similar to the roll-to-roll film forming apparatus in FIGS. 202, which is divided into six zones including a first film formation chamber 203a-1, a second film formation chamber 203a-2, a third film formation chamber 203b, a pretreatment chamber 203c, and a winding chamber 204. It is said. These six zones are also separated by a cooling can roll 212 and a partition wall 205, as in the roll-to-roll film forming apparatus of FIGS. 1 and 2, and each is separated by an independent evacuation system (not shown). Pressure control is possible. A coolant supplied from the outside of the vacuum vessel 201 circulates inside the cooling can roll 212.

  In the first film forming chamber 203a-1 and the second film forming chamber 203a-2, a film forming unit 213a and a film forming unit 213b are provided at positions facing the cooling can roll 212, respectively. The configuration and operating conditions of these film forming means 213a and 213b and the material and film thickness of the metal film formed by these can be determined in the same manner as the roll-to-roll film forming apparatus of FIGS. Therefore, explanation is omitted.

  In the unwinding chamber 202, an unwinding roll 206, an unwinding side guide roll 207a, and an unwinding side tension roll 208a for unwinding the organic resin film F wound in a roll shape are provided. In the winding chamber 204, a winding roll 209, a winding side tension roll 208b, and a winding side guide roll 207b are provided. In the roll-to-roll film forming apparatus shown in FIGS. 1 and 2, the unwind chamber 202 and the winding chamber 204 are provided with dry surface treatment means, but the roll-to-roll film forming apparatus shown in FIG. The unwinding chamber 202 and the winding chamber 204 are not provided with a dry surface treatment means. Instead, as will be described below, the third film formation chamber 203b and the pretreatment chamber 203c are provided with an oxide film formation processing means 211 and a pre-deposition dry surface treatment means 210, respectively.

  More specifically, in the third film formation chamber 203b, an oxide film formation processing unit 211 is provided at a position facing the cooling can roll 212. The oxide film formation processing unit 211 performs an oxide film formation process on the surface of the first metal film formed by the film formation units 213a and 213b to form an oxide film. This suppresses the activity of the fresh metal thin film after the formation of the first metal film in the same manner as the dry surface treatment means 11 and 111 of FIG. 1 and FIG. Problems such as sticking to the surface of the second metal film and wrinkles can be prevented.

  A sputtering apparatus can be used for the oxide film formation processing unit 211. At that time, it is preferable that the inside of the third film formation chamber 203b contains an atmosphere selected from oxygen, water vapor, carbon dioxide, or carbon monoxide, and the rest is made of argon gas. For example, as conditions for mixing argon gas and other gases, the atmospheric pressure in the third film formation chamber 203b is 0.1 Pa to 1 Pa, and oxygen, water vapor, carbon dioxide, or carbon monoxide is 2% to 15%. Contain, and the remainder is argon gas.

  As described above, the post-deposition dry surface treatment atmosphere in the case of performing the sputter deposition preferably contains any one selected from oxygen, water vapor, carbon dioxide, or carbon monoxide. This is because oxygen, water vapor, carbon dioxide, or carbon monoxide serves as an oxygen source and can form an oxide on the surface of the metal thin film. The material and thickness of the oxide film formed by the oxide film formation processing means 211 can be determined in the same manner as in the case of the film formation by the dry surface treatment means 11 and 111 after the film formation, and the description thereof is omitted. .

  Next, the pre-deposition dry surface treatment means 210 provided in the pretreatment chamber 203c will be described. The pre-deposition dry surface treatment means 210 performs dry surface treatment on the organic resin film before the metal film is formed, like the pre-deposition dry surface treatment means 10 and 110 described above. As a specific method of the dry surface treatment before film formation, a known method may be adopted as appropriate according to the purpose. For example, a discharge electrode is installed in the pretreatment chamber 203c, and a DC or AC voltage is applied thereto. A method of forming plasma by applying or irradiating an arbitrary place with a microwave using a waveguide can be given. The pre-deposition dry surface treatment means 210 forms plasma to be used in the film formation means 213a and film formation means 213b of the first film formation chamber 203a-1 and the second film formation chamber 203a-2 at the subsequent stage. You can also.

  With the configuration described above, the organic resin film F unwound from the unwinding roll 206 is guided to the unwinding side guide roll 207a and the tension is controlled by the unwinding side tension roll 208a. It is conveyed while touching along. While the organic resin film F is in contact with the surface of the cooling can roll 212, a first metal film is formed by the film forming means 213a and 213b on the surface opposite to the contacted area. Next, an oxide film is formed on the first metal film by the oxide film formation processing unit 211.

  When the metal film is formed, the organic resin film F is cooled by the cooling can roll 212, so that temperature damage due to a film forming process such as sputtering can be suppressed. Further, since the oxide film is formed while the organic resin film F is in contact with the surface of the cooling can roll 212, the surface of the organic resin film F in contact with the surface of the cooling can roll 212 is The oxide film deposition processing means 211 does not undergo alteration.

  The organic resin film F on which the metal film and the oxide film are formed is taken up by the take-up roll 209 through the take-up side tension roll 208b and the take-up side guide roll 207b. With the above operation, a single area layer substrate in which the first metal film is formed on one surface of the organic resin film F is obtained. Subsequent operations can be performed in the same manner as the roll-to-roll film forming apparatus shown in FIGS. In this way, a double-sided laminated substrate wound in a roll shape can be obtained.

  The organic resin film F used for this invention is not specifically limited, A well-known resin film can be used. For example, low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, or random α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene or the like Polyolefins such as block copolymers, cyclic olefin copolymers, etc., ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, ethylene / vinyl chloride copolymers such as ethylene / vinyl chloride copolymers, polystyrene , Styrenic resins such as acrylonitrile / styrene copolymer, ABS, α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, polymethyl acrylate, polymethacrylic acid Polyvinyl compounds such as methyl, na Iron 6, Nylon 6-6, Nylon 6-10, Nylon 11, Nylon 12 and other polyamides, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other thermoplastic polyesters, polycarbonate, polyphenylene oxide, polylactic acid, etc. It may be a biodegradable resin or a resin of any mixture thereof. Moreover, you may consist of thermosetting resins, such as a polyimide and an epoxy resin.

  The dimensions of the organic resin film F are not particularly limited and can be appropriately determined according to the use, but it is preferable if the thickness is 100 μm or less and the film length is 100 m or more.

  As described above, an oxide film is provided on the surface of the formed first metal film to inactivate it, so that when the second metal film is formed, the winding pressure is high or the metal film Even if there are small protrusions or the surface temperature of the metal film is high, problems such as wrinkles and sticking can be avoided without considering them at all. Thereby, a smooth metal thin film can be neatly formed on both surfaces of the organic resin film. Furthermore, since the thin film laminated substrate wound up in a roll shape is not directly exposed to the atmosphere except for the thin film laminated substrate on the surface, the quality such as the occurrence of pinholes in the thin film and the decrease in adhesion Can be prevented.

[Example 1]
A double-sided laminated substrate was produced using a roll-to-roll film forming apparatus having an ion source as shown in FIG. As the organic resin film F, a polyimide film having a thickness of 38 μm, a width of 50 cm, and a length of 2500 m (Kapton (registered trademark) manufactured by Toray DuPont) was used. The winding roll 9 had a diameter of 8 cm and a width of 80 cm. Moreover, the conveyance speed of the organic resin film F was 6 m / min.

  The sputtering cathode of the film forming means 13a was provided with a nickel chromium alloy target of 20% by mass of chromium, and the sputtering cathode of the film forming means 13b was provided with a copper target. Both of these sputtering cathodes were magnetron sputtering cathodes.

The inside of the vacuum vessel 1 of the roll-to-roll film forming apparatus was depressurized to an ultimate pressure of 10 ⁻⁴ Pa, and then argon was introduced into the film forming chamber 3 so that the pressure became 0.1 Pa. The surface pressure of the organic resin film F was modified by irradiating an ion beam from an ion source as the dry surface treatment means 10 before film formation with the atmospheric pressure of the unwind chamber 2 being 0.15 Pa. Power is applied to the sputtering cathode, sputtering is performed to form the first metal film, and the atmospheric pressure in the winding chamber 4 is set to 0.15 Pa. After the film formation, the ion source as the dry surface treatment means 11 is used. Irradiation with an ion beam forms an oxide film on the surface of the metal film immediately after the formation of the first metal film, inactivates it, winds the organic resin film F around the winding roll 9, and The metal film formation was completed. Thereafter, the vacuum vessel 1 was replaced with argon gas, and then the roll-shaped organic resin film F was removed.

  The surface modification conditions in the dry-type surface treatment means 10 before film formation are changed by performing a preliminary test for each lot change because the product characteristics, particularly the adhesion strength of the metal film, change for each lot of the organic resin film F. Processing was performed after quality conditions were optimized. Moreover, it measured from the change of the film thickness before and behind removal of an oxide film that the film thickness of the oxide film on the surface of a copper thin film layer using the dry surface treatment means 11 after film-forming was 1 nm.

  A roll-shaped organic resin film F having a first metal film formed on one surface is set on the unwinding roll 6 of the vacuum vessel 1 and wound in reverse to the film formation of the first metal film. Then, the second metal film was formed on the other surface. The conveyance speed of the organic resin film F and the input of electric power to the sputtering cathode were formed under the same conditions as those for forming the first metal film. It has been empirically known that the surface modification by the dry surface treatment means 10 before film formation can be effective even with an output of 80% to 100% during the surface modification of one surface. We weakened and processed. Further, since it was during the formation of the second metal film, the dry surface treatment using the dry surface treatment means 11 was not performed after the film formation. As a result, when winding the double-sided laminated substrate on the winding roll 9, no sticking or wrinkle was confirmed.

[Comparative Example 1]
Using the same roll-to-roll film forming apparatus as in Example 1 above, the same as in Example 1 above, except that after the film formation, the deactivation treatment by the formation of the oxide film in the dry surface treatment means 11 is not performed. A first metal film was formed on one surface of the organic resin film F, and a second metal film was formed on the other surface. At this time, the state of failure was investigated by variously changing the transport speed of the organic resin film F during the formation of the second metal film.

  As a result, there was no problem when the organic resin film F was deposited at a transport speed that was 1/2 that of the first metal film, but when transported at a transport speed of 3/4, Partial sticking and wrinkling occurred, and when the film was formed at the same transport speed, sticking occurred halfway and the apparatus stopped due to abnormal tension. That is, it was determined that the safe film formation conveyance speed when the dry surface treatment was not performed after film formation was half the film formation condition of the first metal film.

[Example 2]
A double-sided laminated substrate was manufactured using a roll-to-roll film forming apparatus having an oxide film forming processing means 211 as shown in FIG. The winding roll 209 had an outer diameter of 17 cm and a width of 80 cm. In addition, the used organic resin film F and its conveyance speed were the same as Example 1. Further, the film forming unit 213a and the film forming unit 213b were provided with the same sputtering cathode as in Example 1, and the sputtering cathode of the oxide film forming unit 211 was provided with a copper target. These sputtering cathodes were all magnetron sputtering cathodes.

After reducing the inside of the vacuum vessel 201 of the roll-to-roll film forming apparatus to an ultimate pressure of 10 ⁻⁴ Pa, argon is introduced into the first and second film forming chambers 203 a-1 and 203 a-2 to reduce the pressure to 0. It was set to 1 Pa. On the other hand, in the third film formation chamber 203b, argon containing 5% oxygen was introduced to set the atmospheric pressure to 0.15 Pa. In this state, power is applied to the sputtering cathode, and sputtering is performed to form the first metal film. At the same time, the surface oxide film deposition processing unit 211 applies the power to the surface of the metal film immediately after the first metal film is deposited. An inactive treatment was performed by forming an oxide film. Then, the organic resin film F was wound up on the winding roll 209, and the film formation of the first metal film was completed. Thereafter, the vacuum vessel 201 was replaced with argon gas, and then the roll-shaped organic resin film F was removed.

  The surface modification conditions in the dry surface treatment means 210 before film formation are changed by performing a preliminary test for each lot change because the product characteristics, particularly the adhesion strength of the metal film, change for each lot of the organic resin film F. Processing was performed after quality conditions were optimized. Further, it was confirmed by TEM observation that the thickness of the oxide film on the surface of the copper thin film layer using the oxide film processing means 211 was 2 nm.

  A roll-shaped resin film F on which the first metal film is formed on one surface is set on the unwinding roll 206 of the vacuum vessel 201, and unwinds contrary to the film formation on the first metal film. As a result, the formation of the second metal film on the other surface was started. The conveyance speed of the resin film F and the application of electric power to the sputtering cathode were formed under the same conditions as those for forming the first metal film. It has been empirically known that the surface modification by the dry surface treatment means 210 before film formation is effective even if the output is 80% to 100% during the surface modification of one surface. We weakened and processed. Further, since the second metal film was being formed, the oxide film processing means 211 was not applied. As a result, when the double-sided laminated substrate was wound around the winding roll 209, no sticking or wrinkle was confirmed.

[Comparative Example 2]
Using the same roll-to-roll film forming apparatus as in Example 2 above, an organic resin film is obtained in the same manner as in Example 2 except that the inactivation process is not performed by forming an oxide film in the oxide film processing unit 211. A first metal film was formed on one surface of F, and a second metal film was formed on the other surface. At this time, the state of failure was investigated by variously changing the transport speed of the organic resin film F during the formation of the second metal film.

As a result, there was no problem when the organic resin film F was deposited at a transport speed that was 1/2 that of the first metal film, but when transported at a transport speed of 3/4, Partial sticking and wrinkling occurred, and when the film was formed at the same transport speed, sticking occurred halfway and the apparatus stopped due to abnormal tension. That is, it was determined that the safe film forming conveyance speed when the oxide film processing unit 211 is not used is a half of the film forming condition of the first metal film. In Comparative Example 2, since the oxide film was formed while the organic resin film F was in contact with the surface of the cooling can roll 212, it was generated in the organic resin film F compared to Comparative Example 1. The wrinkles were small and the frequency of wrinkles was low.

1, 201 Vacuum container 2, 202 Unwind chamber 3 Film forming chamber 203a-1, 1st, 2nd film forming chamber 203b 3rd film forming chamber 203c Pretreatment chamber 4, 204 Winding chamber 5, 205 Bulkhead 6, 206 Unwinding roll 7a, 207a Unwinding side guide roll 7b, 207b Winding side guide roll 8a, 208a Unwinding side tension roll 8b, 208b Winding side tension roll 9, 209 Winding roll 10 Dry surface treatment means before film formation (Ion source)
11 Dry surface treatment means (ion source) after film formation
110 Dry surface treatment means (plasma treatment equipment) before film formation
111 Dry surface treatment means (plasma treatment equipment) after film formation
210 Dry surface treatment means before film formation 211 Oxide film formation treatment means 12, 212 Cooling can rolls 13a, 13b Film formation means 213a, 213b Film formation means 14a Unwinding side auxiliary guide roll 14b Winding side auxiliary guide roll F Organic Resin film

Claims (9)

  A method of forming a double-sided laminated substrate in which a metal film is formed on both sides of an organic resin film conveyed by a roll-to-roll under a reduced pressure atmosphere, wherein the first side of the organic resin film is formed by dry plating. After forming a first metal film and forming an oxide film on the surface of the first metal film by dry surface treatment, a second metal film is formed on the other surface of the organic resin film by a dry plating method. A film forming method characterized by:   The film forming method according to claim 1, wherein the dry surface treatment is an ion beam irradiation treatment or a plasma treatment.   2. The film forming method according to claim 1, wherein the dry surface treatment is a process of forming an oxide film on a surface of the first metal film while cooling the organic resin film.   The film forming method according to claim 1, wherein the dry surface treatment atmosphere contains any one selected from oxygen, water vapor, carbon dioxide, and carbon monoxide.   5. The composition according to claim 1, wherein the dry surface treatment is performed so that a film thickness of the oxide film is ½ or less of a film thickness of the first metal film. Membrane method.   The organic resin film is conveyed while one surface thereof is in contact with the surface of the cooling can roll, and when the organic resin film is in contact with the surface of the cooling can roll, the surface on the opposite side of the contact region 6. The film forming method according to claim 1, wherein a metal film is formed on the substrate.   The said 2nd metal film is formed in the surface on the opposite side of the area | region which has contacted when the said oxide film is contacting the surface of the said cooling can roll, The said 6th metal film is characterized by the above-mentioned. 2. The film forming method described in 1.   A roll-to-roll film forming apparatus comprising a film forming means for forming a metal film on one side of an organic resin film conveyed by a roll-to-roll under a reduced pressure atmosphere by a dry plating method, A roll comprising a dry surface treatment means for forming an oxide film on the surface of the metal film at a position along the transport path of the resin film and behind the film forming means in the transport direction. Two-roll deposition system.   9. The roll-to-roll film forming apparatus according to claim 8, wherein the dry surface treatment means is provided at a position facing the cooling can roll.

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