JP2011255611A - Method for manufacturing heat-resistant resin film with metal base layer with dielectric resin film and for manufacturing heat-resistant resin film with metal film and apparatus for manufacturing heat-resistant resin film with metal base layer with dielectric resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a heat-resistant resin film with a metal base layer, etc. having excellent adhesion wherein no pin-hole is observed and oxidation of a metal base layer can be prevented.SOLUTION: A manufacturing method of a heat-resistant resin film with a metal base film comprises the process step of forming a dielectric film (AlO) on the both surfaces of a resin film 8 transported by a role-to-role system using an atomic layer deposition (ALD) method, the process step of forming a metal base layer (Cu) on each dielectric film by a spattering web coater, and the winding process step of winding up a long-size heat-resistant resin film wherein a metal base layer is formed on each dielectric film on a winding-up role, in which the process steps are conducted continuously, whereby formation of a pin-hole is hardly observed even when a thin film thickness of the metal base layer is set forth because the metal base layer is formed on a dielectric film having no pin-hole which is formed by an ALD method and supply of oxygen from a resin film can be prevented so as to suppress oxidation of the metal base layer and suppress lowering adhesion.

Description

  The present invention relates to a heat-resistant resin film with a metal film applied to a flexible wiring board and a heat-resistant resin film with a metal base layer used for the production of the heat-resistant resin film with a metal film, and in particular, due to the resin film. For manufacturing a heat-resistant resin film with a metal base layer having a dielectric film that prevents oxidation of the metal base layer, and a method for manufacturing a heat-resistant resin film with a metal film using the heat-resistant resin film with a metal base layer And the manufacturing apparatus of the said heat resistant resin film with a metal base layer is related.

  Liquid crystal panels, notebook computers, digital cameras, mobile phones, etc. use many types of flexible wiring boards obtained by coating a metal film on a heat-resistant resin film. A heat-resistant resin film with a metal film in which a metal film is formed on one side or both sides is used. In addition, since the heat-resistant resin film with a metal film may be used by being folded, it is necessary that the adhesion of the metal film to the heat-resistant resin film is high, and further, along with the finer and higher density of the wiring pattern. In addition, since there is a possibility of disconnection if a pinhole is present in the metal film, it is also required that there is no pinhole.

  And as a manufacturing method of this kind of heat-resistant resin film with a metal film, conventionally, a method of manufacturing by attaching a metal foil to a heat-resistant resin film with an adhesive, coating the metal foil with a heat-resistant resin solution and drying it. And a method of forming a metal film on a heat-resistant resin film by vacuum deposition (vacuum deposition, sputtering, ion plating, ion beam sputtering, etc.) or wet plating Etc. are known.

  In addition, as a third manufacturing method using a vacuum film formation method or a wet plating method, in Patent Document 1, a heat-resistant resin with a metal film is formed using a sputtering method capable of forming a metal film having a low film formation speed but excellent adhesion. A method for producing a film is disclosed, and in Patent Document 2, a thin metal base layer is first formed using a sputtering method capable of forming a metal film having a low film formation rate but excellent adhesion, and then formed. A method of efficiently producing a heat-resistant resin film with a metal film by forming a thick metal film on the metal base layer using a wet plating method having a high speed is disclosed. Patent Document 1 also discloses a method using two types of sputtering targets in order to further increase the adhesion of the metal film. That is, a method has been proposed in which a thin metal seed layer is first formed using monel metal or the like as a sputtering target, and then a thick metal film is formed on the metal seed layer using copper or the like as a sputtering target.

  And since the manufacturing method of patent document 2 which uses the wet plating method with a high film-forming speed | rate and sputtering method with a slow film-forming speed | velocity is excellent compared with the method of the patent document 1 using only a sputtering method, patent document The manufacturing method described in 2 is widely used.

  By the way, the method of patent document 2 which forms a metal base layer first using the sputtering method with a slow film-forming speed | rate, and then forms a metal film on the said metal base layer using the wet-plating method with a high film-forming speed | velocity. By adopting it, it becomes possible to efficiently produce a heat-resistant resin film with a metal film excellent in adhesion of the metal film, but when carrying out this method, the metal base layer by sputtering and the wet plating method It is important to set the film thickness ratio of the metal film. That is, the thickness of the metal base layer formed by the sputtering method is required to suppress the generation of pinholes and obtain good adhesion. This is because if the thickness of the metal base layer formed by the sputtering method exceeds the required thickness, even if a small pinhole is present, the pinhole is blocked as the metal base layer grows. is there. However, since the deposition rate of the metal base layer by the sputtering method is about an order of magnitude slower than the deposition rate of the wet plating method, the metal base layer having a thickness greater than that required by the sputtering method must be formed. The production efficiency of the heat-resistant resin film with a metal film will be deteriorated. Therefore, from the viewpoint of manufacturing efficiency, there has been a demand for a new method capable of forming a metal base layer without a pinhole even when the film thickness is small.

Further, it is known that when a resin film on which a metal film is formed is left for a long period of time, the metal film is oxidized by oxygen contained in the resin film to reduce its adhesion, for example, an absorption multilayer film ND. In the field of filters, a method of forming a metal film after forming a dielectric film such as SiO ₂ on a resin film is employed in order to prevent oxidation of the metal film (see Patent Document 3). Therefore, in the heat resistant resin film with a metal film applied to a flexible wiring board and the heat resistant resin film with a metal base layer used for the production of the heat resistant resin film with a metal film, the oxidation of the metal film or the metal base layer is also performed. There is a demand for a new manufacturing method that can prevent this.

Japanese Patent No. 3447070 Japanese Patent No. 3570802 International Publication WO2007 / 083833

Journal of applied physics 97,121301 (2005)

  The present invention has been made paying attention to such problems, and the object of the present invention is to provide a metal base layer that is excellent in adhesion of the metal base layer, has no pinholes, and prevents oxidation of the metal base layer. The present invention provides a method for efficiently producing a heat-resistant resin film with a metal base layer, a method for producing a heat-resistant resin film with a metal film using the heat-resistant resin film with a metal base layer, and the heat-resistant resin film with a metal base layer. It is to provide a manufacturing apparatus.

  Therefore, in order to solve the above-mentioned problems, the present inventor paid attention to the atomic layer deposition (ALD) method described in Non-Patent Document 1 and tried to adopt it.

  That is, in the ALD method, a source gas containing an element constituting a molecular layer (atomic layer) is alternately introduced into a vacuum apparatus, and molecules adsorbed on the outermost surface of the deposition target and a source material to be introduced next. A method of forming a molecular layer by reaction with a gas (sometimes referred to as bottom-up film formation). Although the film formation rate is slower than the sputtering method described above, it was ejected from the target as in the sputtering method. Since it is not a method of depositing and stacking fine particles or clusters on a film formation body, a thin film without pinholes can be formed, and a thin film can be formed even in minute gaps without being affected by irregularities on the surface of the film formation body.

  Therefore, before the metal base layer is formed, the dielectric film for preventing oxidation caused by the resin film is first formed on both surfaces of the heat-resistant resin film (film formation body) by the ALD method, and then by the sputtering method. It has been found that by forming a metal base layer on the dielectric film, it is possible to form a metal base layer that is excellent in adhesion, has no pinholes, and prevents oxidation. The present invention has been completed by such technical discovery.

That is, the invention according to claim 1
A dielectric film having a metal base layer formed by sputtering on each side of a long heat-resistant resin film and a metal film formed by wet plating on each metal base layer is provided. In the manufacturing method of the heat resistant resin film with a metal base layer having,
The long heat-resistant resin film unwound from the unwinding roll is transported by a roll-to-roll method and wound around the winding roll, and atomic layer deposition is performed on the transport path between the unwinding roll and the winding roll ( A first film forming step of forming dielectric films on both surfaces of the heat resistant resin film by an Atomic Layer Deposition (ALD) method;
A second film forming step of forming a metal base layer on one dielectric film by a first sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film is wound on the transport path;
A metal base layer is formed on the other dielectric film by a second sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film having a metal base layer formed on the one dielectric film is wound on the transport path. A third film forming step for forming a film;
A winding process in which a long heat-resistant resin film in which a metal base layer is formed on each dielectric film is wound on a winding roll;
And the first film forming process, the second film forming process, and the third film forming process are continuously performed.

The invention according to claim 2
In the manufacturing method of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on invention of Claim 1,
In the first film forming process, at least one or more pairs of first reaction chambers for introducing the first reaction gas and second reaction chambers for introducing the second reaction gas are alternately arranged in the conveyance direction of the heat resistant resin film. It is characterized by using a body film forming means,
The invention according to claim 3
In the manufacturing method of the heat resistant resin film with a metal base layer which has a dielectric film based on the invention of Claim 1 or 2,
The dielectric film is composed of at least one oxide film or nitride film selected from Si, Al, Zr, Hf, Ti, Ta, and Nb, and the metal base layer is Cu or a Cu-based alloy. It is composed of one kind selected from
The invention according to claim 4
In the manufacturing method of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on the invention in any one of Claims 1-3,
A metal seed layer selected from Ni or Ni alloy and deposited by the sputtering web coater is interposed between the dielectric film and the metal base layer,
The invention according to claim 5
In the manufacturing method of the heat resistant resin film with a metal base layer which has a dielectric film concerning the invention in any one of Claims 1-4,
The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film.

Next, the invention according to claim 6 is:
In the method for producing a heat-resistant resin film with a metal film,
A metal film of the same type as the metal base layer by a wet plating method on each metal base layer of the heat-resistant resin film with a metal base layer having a dielectric film obtained by the production method according to claim 1. Are formed respectively.

The invention according to claim 7
It has a dielectric film formed by atomic layer deposition (ALD) on both sides of a long heat-resistant resin film, and a metal base layer formed by sputtering on each dielectric film In the manufacturing equipment for heat resistant resin film with metal base layer,
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
In the first decompression chamber, an unwinding roll for unwinding the long heat-resistant resin film, a first reaction chamber for introducing the first reaction gas in the conveying direction of the unrolled heat-resistant resin film, and a second A means for forming a dielectric film in which at least one or more sets of second reaction chambers for introducing a reaction gas are alternately arranged; and
The second decompression chamber has a can roll and a sputter cathode around which the heat resistant resin film carried through the opening of the partition wall is wound, and a metal base layer on one dielectric film of the heat resistant resin film A first sputtering web coater for forming a film, a can roll having a heat-resistant resin film having a metal base layer formed on the one dielectric film and a sputtering cathode, and the other of the heat-resistant resin film A second sputtering web coater for forming a metal base layer on the dielectric film, and a winding roll for winding a long heat-resistant resin film in which the metal base layer is formed on each dielectric film are provided. As well as
A plurality of roll groups constituting a roll-to-roll system conveying means are respectively provided in the first decompression chamber and the second decompression chamber over the conveyance direction of the heat resistant resin film,
The invention according to claim 8 provides:
In the manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on invention of Claim 7,
The dielectric film formed by the dielectric film forming means is composed of at least one oxide film or nitride film selected from Si, Al, Zr, Hf, Ti, Ta, Nb, and The metal base layer formed by the first sputtering web coater and the second sputtering web coater is composed of one kind selected from Cu or Cu-based alloy,
The invention according to claim 9 is:
In the manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on invention of Claim 7,
A metal seed layer selected from Ni or Ni alloy and interposed between the dielectric film and the metal base layer is formed by a first sputtering web coater and a second sputtering web coater, respectively,
The invention according to claim 10 is
In the manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on the invention in any one of Claims 7-9,
The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film.

A method for producing a heat-resistant resin film with a metal base layer having a dielectric film according to claims 1 to 5,
The long heat-resistant resin film unwound from the unwinding roll is transported by a roll-to-roll method and wound around the winding roll, and atomic layer deposition is performed on the transport path between the unwinding roll and the winding roll ( A first film forming step of forming dielectric films on both surfaces of the heat resistant resin film by an Atomic Layer Deposition (ALD) method;
A second film forming step of forming a metal base layer on one dielectric film by a first sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film is wound on the transport path;
A metal base layer is formed on the other dielectric film by a second sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film having a metal base layer formed on the one dielectric film is wound on the transport path. A third film forming step for forming a film;
A winding process in which a long heat-resistant resin film in which a metal base layer is formed on each dielectric film is wound on a winding roll;
And the first film-forming process, the second film-forming process, and the third film-forming process are continuously performed.

  And since a dielectric film without pinholes can be formed on both surfaces of the heat-resistant resin film by the atomic layer deposition (ALD) method in the first film forming step, the sputtering method is used in the second film forming step and the third film forming step. The thickness of the metal base layer formed on each dielectric film does not need to be set as large as the thickness that closes the pinhole as in the conventional method, and the heat resistance resin film is formed by the action of each dielectric film. It is possible to prevent the resulting oxidation of the metal base layer.

Moreover, the manufacturing method of the heat resistant resin film with a metal film which concerns on Claim 6 is as follows.
A metal film of the same type as the metal base layer by a wet plating method on each metal base layer of the heat-resistant resin film with a metal base layer having a dielectric film obtained by the production method according to claim 1. Since the heat-resistant resin film with a metal base layer can be produced efficiently, the heat-resistant resin film with a metal film can be produced efficiently.

Next, the manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on Claims 7-10 is,
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
In the first decompression chamber, an unwinding roll for unwinding the long heat-resistant resin film, a first reaction chamber for introducing the first reaction gas in the conveying direction of the unrolled heat-resistant resin film, and a second A means for forming a dielectric film in which at least one or more sets of second reaction chambers for introducing a reaction gas are alternately arranged; and
The second decompression chamber has a can roll and a sputter cathode around which the heat resistant resin film carried through the opening of the partition wall is wound, and a metal base layer on one dielectric film of the heat resistant resin film A first sputtering web coater for forming a film, a can roll having a heat-resistant resin film having a metal base layer formed on the one dielectric film and a sputtering cathode, and the other of the heat-resistant resin film A second sputtering web coater for forming a metal base layer on the dielectric film, and a winding roll for winding a long heat-resistant resin film in which the metal base layer is formed on each dielectric film are provided. As well as
Since a plurality of roll groups constituting a roll-to-roll system conveying means are provided in the first decompression chamber and the second decompression chamber over the conveyance direction of the heat resistant resin film,
Using this manufacturing apparatus, a heat resistant resin film with a metal base layer having a dielectric film that has excellent adhesion to the metal base layer, has no pinholes, and prevents oxidation of the metal base layer is efficiently and reliably manufactured. It becomes possible.

Sectional drawing which shows schematic structure of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on this invention. Sectional drawing which shows schematic structure of the heat resistant resin film with a metal film which concerns on this invention. Explanatory drawing which shows schematic structure of the manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric film which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, a heat resistant resin film with a metal base layer having a dielectric film according to the present invention includes a heat resistant resin film 1 and an atomic layer deposition (Atomic Layer Deposition) on both surfaces of the heat resistant resin film 1 as shown in FIG. : ALD) method, and a metal base layer 3 formed on the surface of each dielectric film 2 by a sputtering method.

  Moreover, as shown in FIG. 2, the heat resistant resin film with a metal film using the heat resistant resin film with a metal base layer is formed on the surface of the metal base layer of the heat resistant resin film with a metal base layer. 4 has a structure in which each film is formed. That is, the heat resistant resin film 1, the dielectric film 2 formed on both surfaces of the heat resistant resin film 1 by an atomic layer deposition (ALD) method, and the metal formed on each dielectric film 2 by a sputtering method The base layer 3 is composed of a metal film 4 formed on each metal base layer 3 by a wet plating method.

  Whether to use the heat-resistant resin film with a metal base layer shown in FIG. 1 or the heat-resistant resin film with a metal film shown in FIG. 2 depends on the method of forming a wiring pattern (subtractive method or semi-additive method) described later. Is appropriately selected.

  The precursor before the metal film 4 is formed, that is, the heat-resistant resin film 1, the dielectric film 2 formed on both surfaces of the heat-resistant resin film 1 by an atomic layer deposition (ALD) method, The precursor composed of the metal base layer 3 formed by sputtering on the dielectric film 2 is a heat resistant resin film with a metal base layer having the dielectric film according to the present invention.

  By the way, since the dielectric film 2 formed by the atomic layer deposition (ALD) method has high surface activity, if the heat-resistant resin film 1 having the dielectric film 2 formed on both surfaces is wound up as it is, The dielectric film 2 may stick to the surface of the heat-resistant resin film 1 that comes into contact. Therefore, in the method for producing a heat-resistant resin film with a metal base layer having a dielectric film according to the present invention, a first film forming step of forming a dielectric film on both surfaces of the heat-resistant resin film, and one dielectric It is necessary to continuously perform the second film forming step for forming the metal base layer on the film and the third film forming step for forming the metal base layer on the other dielectric film.

  In the film formation by the atomic layer deposition (ALD) method in the first film formation process, simultaneous film formation on both surfaces of the heat resistant resin film 1 is possible. This is because the ALD method is a method of depositing monoatomic (monomolecular) layers one by one. Moreover, since it is a method of depositing monoatomic (monomolecular) layers one by one, as described above, it is not affected by unevenness on the surface of the heat-resistant resin film 1 (film formation target), and there are no pinholes in minute gaps. A dielectric film can be formed and antioxidation of the metal base layer is expected by the action of the dielectric film having no pinholes.

  Examples of the material constituting the dielectric film include at least one oxide film or nitride film selected from Si, Al, Zr, Hf, Ti, Ta, and Nb. Examples of the constituent material include Cu and Cu-based alloys.

  Further, a metal seed layer selected from Ni or Ni alloy and formed by a sputtering web coater may be interposed between the dielectric film and the metal base layer. The thickness of the metal seed layer is desirably 3 nm to 50 nm, and the thickness of the metal base layer composed of Cu or a Cu-based alloy is desirably 10 nm to 1 μm. The metal seed layer is expected to have an effect of preventing oxidation of the metal base layer, like the dielectric film. In addition, regarding the film thickness of the metal film formed by the wet plating method on the metal base layer of the heat resistant resin film with a metal base layer having a dielectric film, the total thickness of the metal base layer and the metal film is large. Both are preferably 18 μm or less.

  The heat-resistant resin film of the present invention is a resin selected from a polyimide film, a polyamide film, a polyester film, a polytetrafluoroethylene film, a polyphenylene sulfide film, a polyethylene naphthalate film, or a liquid crystal polymer film. The film is preferable because it has flexibility as a flexible substrate with a metal film, strength required for practical use, and electrical insulation suitable as a wiring material.

  Hereinafter, the “ALD method”, “sputtering web coater”, and “manufacturing apparatus for heat resistant resin film with metal base layer” used in the present invention will be described in detail.

1. ALD method Atomic Layer Deposition (ALD) method is a film deposition method in which source gases containing elements constituting molecular layers (atomic layers) are alternately introduced into a vacuum device. This is a method in which a single atom (monomolecular) layer is deposited by a reaction between a molecule adsorbed on the outermost surface of the body and a source gas introduced next, and the film thickness of the layer can be controlled at the atomic layer level.

  The ALD method is a method in which film formation starts while depositing a single atom (monomolecular) layer from the film formation side. As described above, pinholes are formed on the heat resistant resin film (film formation). It is possible to form no dielectric film. In this ALD method, in the above-described vacuum film formation method (vacuum deposition method, sputtering method, ion plating method, ion beam sputtering method, etc.), the metal clusters fly over the film formation body, Since the adhesion and the clusters are combined to form a film, it is greatly different from the vacuum film formation method which has the possibility of creating pinholes between the clusters. In addition, even on the surface of the film to be deposited, which is difficult to form by sputtering or vacuum deposition, which has high straightness, it is possible to form a uniform film by ALD, and it is included in the heat-resistant resin film. A film is uniformly formed in the shade of filler particles that may appear on the surface or on the scratches present on the surface of the heat resistant resin film. Furthermore, since the raw material is a gas in the ALD method, there is no occurrence of splash (the film raw material jumps to the film formation body while it is solidified) frequently generated by the sputtering method or the vacuum evaporation method. Accordingly, there is no phenomenon in which the splash adheres to the film being formed and falls off to form a pinhole. In addition, the vacuum apparatus used in the ALD method does not require an expensive power supply unit or the like necessary for the vacuum apparatus used in the PVD method or the CVD method, and the film formation cost is lower than that of the conventional film formation method. Reduction can also be achieved.

  In the ALD method, a first reaction gas (source gas) and a second reaction gas (source gas) containing each of the elements constituting the molecular layer are alternately introduced into a vacuum apparatus (reaction chamber) as described below. The A to H steps constitute one cycle, and the film thickness is adjusted according to the number of cycles.

A. First reaction gas (raw material gas) is introduced into the vacuum device. C. First reaction gas is chemisorbed on the outermost surface of the deposition target. D. Saturation of the outermost surface of the deposition target with the first reaction gas Evacuate excess first reactant gas and by-products from the vacuum apparatus E. F. Second reaction gas (raw material gas) is introduced into the vacuum device. G. First reaction gas and second reaction gas adsorbed on the outermost surface of the deposition target react. The outermost surface of the deposition target is saturated with the second reaction gas. Exhaust excess second reaction gas and by-products from the vacuum system

In the ALD method, oxide films such as SiO ₂ , Al ₂ O ₅ , ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , TiO ₂ , nitride films such as AlN, TaN, TiN, TaSiN, TiSiN, Cu, A metal film such as Ru, Ir, Ni, or Pt, a fluoride film such as CaF ₂ , SrF ₂ , or MgF ₂ , or a compound film such as GaAs, InP, or GaP can be formed.

For example, in the case of forming an Al ₂ O ₃ monoatomic (monomolecular) layer that is most frequently deposited by the ALD method, one cycle is completed in the following four steps.

(1) Water molecules as the first reaction gas are introduced to adsorb OH groups on the outermost surface of the film formation target.
(Reaction after the first layer)
2H ₂ O +: O—Al (CH ₃ ) ₂ →: Al—O—Al (OH) ₂ + 2CH ₄
(2) Purge and exhaust excess water molecules.
(3) TMA [Trimethyl Aluminum: Al (CH ₃ ) ₃ ] gas, which is the second reaction gas (raw material gas) of the Al ₂ O ₃ film, is introduced. TMA molecules react with OH groups to generate CH ₄ gas.
(First layer reaction)
Al (CH ₃ ) ₃ +: O—H →: O—Al (CH ₃ ) ₂ + CH ₄
(Reaction after the first layer)
Al (CH ₃ ) ₃ +: Al—O—H →: Al—O—Al (CH ₃ ) ₂ + CH ₄
(4) Purge and exhaust excess TMA gas and CH ₄ gas.

Since an Al ₂ O ₃ film of about 0.1 nm is formed in these four steps, the above four steps are repeated until the required film thickness is reached, and the film thickness is increased.

  In the ALD method, in order to promote the reaction, it is preferable to heat the film formation body (100 to 300 ° C.) or perform plasma irradiation.

2. Sputtering web coater The heat resistant resin film with a metal film according to the present invention was formed by atomic layer deposition (ALD) on both surfaces of the heat resistant resin film 1 and the heat resistant resin film 1 as shown in FIG. The dielectric film 2 includes a metal base layer 3 formed on each dielectric film 2 by a sputtering method, and a metal film 4 formed on each metal base layer 3 by a wet plating method.

  And in the manufacturing method of the heat resistant resin film with a metal base layer concerning this invention, the metal seed layer interposed between the metal base layer 3 and the dielectric film 2 and the metal base layer 3 as needed is formed into a film. As a means, a sputtering web coater capable of efficiently forming a metal film on the long film surface is applied.

  The sputtering web coater has a can roll which is arranged on a conveyance path between a roll and a take-up roll of a heat-resistant resin film and is water-cooled, and a sputtering cathode which is arranged in the vicinity of the outer peripheral surface of the can roll. In addition, since the sputtering film formation is performed in a state where the heat resistant resin film on which the dielectric film is formed is wound around the can roll, the thermal damage of the heat resistant resin film due to the plasma during the film formation can be reduced.

  Moreover, the tension roll of the heat resistant resin film is maintained by a powder clutch or the like for the unwinding roll and the winding roll, and the long heat resistant resin film is unwound from the unwinding roll by the rotation of the can roll. It is wound on a roll. In addition, it is preferable to use a plate-like target for the sputtering formation of the metal base layer and, if necessary, the metal seed layer interposed between the dielectric film and the metal base layer, but when a plate-like target is used, Nodules (foreign material growth) may occur on the target. Therefore, it is possible to use a cylindrical rotary target in which nodule (foreign material growth) is not generated and the target is used efficiently.

3. Manufacturing apparatus for heat-resistant resin film with metal base layer having dielectric film Dielectric film formed on both sides of long heat-resistant resin film by atomic layer deposition (ALD) method, and sputtering on each dielectric film An apparatus for producing a heat-resistant resin film with a metal base layer having a dielectric film according to the present invention, each having a metal base layer formed by a method, includes a first decompression chamber and a first decompression chamber via a partition wall. A second decompression chamber is provided adjacent to the first decompression chamber, the unwinding roll for unwinding the long heat-resistant resin film, and the conveying direction of the unrolled heat-resistant resin film. There is provided a dielectric film forming means in which at least one or more pairs of first reaction chambers for introducing the first reaction gas and second reaction chambers for introducing the second reaction gas are alternately arranged, and the second decompression There is a partition opening in the room A first sputtering web coater that has a can roll and a sputtering cathode around which a heat-resistant resin film that is carried in is wound and has a sputtering base and forms a metal base layer on one dielectric film of the heat-resistant resin film; Second sputtering in which a metal base layer is formed on the other dielectric film of the heat resistant resin film, having a can roll and a sputtering cathode around which the heat resistant resin film having a metal base layer formed on the dielectric film is wound A web coater and a take-up roll for winding a long heat-resistant resin film in which a metal base layer is formed on each dielectric film are provided, and a roll-to-roll transport means is provided. A plurality of roll groups to be configured are provided in the first decompression chamber and the second decompression chamber, respectively, across the conveying direction of the heat resistant resin film. It is characterized in that it is.

  Here, the ALD method is a method in which a film is originally formed while replacing a reactive gas with respect to a stationary deposition target. Therefore, in order to form a dielectric film by the ALD method on a long heat-resistant resin film that is continuously conveyed, in the manufacturing apparatus according to the present invention, the conveyance direction of the heat-resistant resin film in the first decompression chamber described above. The first reaction chamber for introducing the first reaction gas and the second reaction chamber for introducing the second reaction gas are alternately arranged in at least one set. In the manufacturing apparatus according to the present invention, the first decompression chamber in which the first reaction chamber for introducing the first reaction gas and the second reaction chamber for introducing the second reaction gas are alternately arranged in at least one or more pairs. When the heat resistant resin film passes through the region, a dielectric film is formed while each reaction of the ALD method described above is performed in each reaction chamber.

  Further, in the manufacturing apparatus according to the present invention, the first decompression chamber in which the dielectric film is formed by the ALD method, the metal base layer by the sputtering method, and the metal interposed between the dielectric film and the metal base layer as necessary Since the gas pressure suitable for film formation is different from that in the second decompression chamber where the seed layer is formed, each decompression chamber is partitioned by the partition wall, and the gas pressure suitable for each film formation is maintained by differential exhaust. There is a need. In the ALD method, it is desirable to heat the film formation body or perform plasma irradiation as described above in order to promote the reaction. However, in consideration of uniformly heating the heat-resistant resin film that is continuously conveyed, it is more preferable to perform plasma irradiation.

  Next, an embodiment of the manufacturing apparatus according to the present invention is shown in FIG.

  That is, as shown in FIG. 3, a manufacturing apparatus 5 for a heat-resistant resin film with a metal base layer having a dielectric film according to the present invention includes a first decompression chamber 7 in which a dielectric film is formed by ALD. In addition, there is provided a metal base layer by sputtering provided adjacently through a partition wall 41 having an opening 42, and a second decompression chamber 6 in which a metal seed layer is formed if necessary. Further, the gas pressure suitable for film formation differs between the first decompression chamber 7 where the dielectric film is formed by the ALD method and the second decompression chamber 6 where the metal base layer or the like is formed by the sputtering method. Therefore, each region is partitioned by the partition wall 41 having the opening 42 and differential exhaust is performed. It is also possible to increase the airtightness by sandwiching the heat resistant resin film 8 between two rolls at the opening 42 portion of the partition wall 41.

  Moreover, in the said 1st decompression chamber 7, the 1st reaction gas is introduce | transduced over the unwinding roll 9 which unwinds the elongate heat resistant resin film 8, and the conveyance direction of the unrolled heat resistant resin film 8. Three sets of the first reaction chamber and the second reaction chamber for introducing the second reaction gas are alternately arranged (that is, the first reaction chamber 14, 16, 18 and the second reaction chamber 15, 17, 19), In addition, the heat-resistant resin film 8 carried through the opening 42 of the partition wall 41 is wound around the second decompression chamber 6 and the water roll-cooled can roll 11 and the four magnetron sputtering cathodes 20, A first sputtering web coater having 21, 22, 23 and forming a metal base layer or the like on one dielectric film of the heat-resistant resin film 8, and forming a metal base layer or the like on the one dielectric film. Membrane heat-resistant resin film It has a can roll 12 and a magnetron sputtering cathode 24, 25, 26, 27 wound with water and temperature-cooled, and a metal base layer is formed on the other dielectric film of the heat resistant resin film 8. A second sputtering web coater to be filmed, and a take-up roll 10 for winding a long heat-resistant resin film 8 in which a metal base layer or the like is formed on each dielectric film. A plurality of free rolls 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 constituting the to-roll type transport means are in the transport direction of the heat resistant resin film 8 The first decompression chamber 7 and the second decompression chamber 6 are provided respectively.

  The long heat-resistant resin film 8 is unwound from the unwinding roll 9 and wound up by the winding roll 10. The unwinding roll 9 and the winding roll 10 are kept in tension balance by a powder clutch or the like, and the heat-resistant resin film 8 is conveyed by the rotation of the water-cooled temperature-controlled can rolls 11 and 12. Further, the above-described free rolls 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 having no drive unit are provided between the unwinding roll 9 and the winding roll 10. When the control is performed to bring the heat-resistant resin film 8 into close contact with the can rolls 11 and 12 by tension, a tension sensor may be attached to the free rolls 31, 32, 37, and 38. Moreover, when performing control which makes the heat resistant resin film 8 contact | adhere to the can rolls 11 and 12 by differential speed, the free rolls 31, 32, 37, and 38 may become a drive roll.

  In order to increase the adhesion between the heat-resistant resin film and the dielectric film, argon gas, oxygen gas, or the like is introduced into the first decompression chamber 7 at a position before the dielectric film is formed by the ALD method. It is also possible to arrange the surface treatment unit 13 for performing the plasma treatment or the ion beam treatment.

  The heat-resistant resin film 8 whose both surfaces are cleaned and activated by the surface treatment unit 13 includes the first reaction chamber 14 into which the first reaction gas is introduced and the second reaction chamber into which the second reaction gas is introduced. 15, a first reaction chamber 16 into which a first reaction gas has been introduced, a second reaction chamber 17 into which a second reaction gas has been introduced, a first reaction chamber 18 into which a first reaction gas has been introduced, and a second reaction gas By passing through the second reaction chamber 19 in which is introduced, the above-described reaction by the ALD method occurs, and a dielectric film of a triatomic (molecular) layer is formed on both sides simultaneously. In order to increase the atomic layer of the dielectric film, the first reaction chamber into which the first reaction gas is introduced and the second reaction chamber into which the second reaction gas is introduced as one set are added in units. Good.

  Next, the heat-resistant resin film 8 having a dielectric film formed on both sides was carried into the second decompression chamber 6 from the first decompression chamber 7 through the opening 42 of the partition wall 41, and the temperature of the water-cooled resin film 8 was adjusted. It is conveyed to the film-forming region of the first sputtering web coater and the second sputtering web coater each having a can roll and four magnetron sputtering cathodes. In the film formation region of the sputtering web coater, the magnetron sputtering cathodes 20, 21, 22, and 23 to which a metal target such as a metal base layer is attached are wound around a can roll 11 that is water-cooled and temperature-controlled. Four magnetron sputtering devices in which a metal base layer or the like is formed on the first film formation surface (on one dielectric film) of the heat resistant resin film 8 and a metal target for forming the metal base layer or the like is further attached. A metal base layer or the like is formed on the second film-forming surface (on the other dielectric film) of the heat-resistant resin film 8 wound on the can roll 12 which is temperature-cooled using the cathodes 24, 25, 26 and 27. After the film formation, the heat-resistant resin film 8 in which the metal base layer or the like is formed on each dielectric film is wound around the take-up roll 10 according to the present invention. Heat-resistant resin film with the metal base layer having a conductor film is obtained.

  And in the heat-resistant resin film with a metal base layer having a dielectric film manufactured in this way, the dielectric film is formed by the ALD method, so there may be pinholes in the metal base layer. Absent. The present inventor infers the reason why no pinhole is present in the metal base layer as follows. First, since film formation proceeds at the atomic level in the ALD method, all the convex and concave portions of the heat-resistant resin film can be completely covered with the dielectric film. Then, since the metal base layer is formed by sputtering on the entire surface of the dielectric film that has a high surface activity while maintaining a vacuum, there is no pinhole in the metal base layer. I guess. On the other hand, when the metal base layer is formed by the sputtering method without forming the dielectric film by the ALD method, the unevenness in the heat-resistant resin film is caused by the high directivity of the sputtered particles. Since it is difficult to completely cover all the parts with the metal base layer (when the metal seed layer is provided, the metal seed layer and the metal base layer), the uncovered part is one of the causes of pinholes. It is thought that it has become.

  In addition, about the heat resistant resin film with a metal base layer which has the obtained dielectric film, you may carry out a wiring process so that it may mention later, and also performs a wet plating process on a metal base layer, and has a metal film. You may process into a heat-resistant resin film.

  And when forming a metal film using a wet plating method on the metal base layer of the heat-resistant resin film with a metal base layer having a dielectric film, electroless plating is used as the primary plating. There are cases where the treatment is performed and a wet plating method such as an electrolytic plating treatment is combined as the secondary plating. The wet plating process may employ various conditions of a conventional wet plating method. Further, by further forming a metal film on the metal base layer formed on the dielectric film having no pinholes, there is no pinhole and oxidation of the metal base layer is prevented with excellent adhesion. It becomes possible to obtain a heat-resistant resin film with a metal film satisfying the merit of manufacturing cost.

  Using the heat-resistant resin film with a metal film thus obtained, a wiring pattern is individually formed on at least one surface of the heat-resistant resin film with a metal film. In addition, via holes for interlayer connection can be formed at predetermined positions and used for various purposes. More specifically, (1) a high-density wiring pattern is individually formed and used on at least one surface of a flexible sheet. (2) A via hole penetrating the wiring layer and the flexible sheet is formed on the flexible sheet on which the wiring layer is formed. (3) In some cases, the via hole is filled with a conductive material to make the hole conductive.

  And as a formation method of the said wiring pattern, what is called a known subtractive method or a semiadditive method can be utilized.

  In the subtractive method, a resist layer such as a dry film is provided on the surface of the metal film of the heat-resistant resin film with a metal film, a mask having a predetermined wiring pattern is provided on the resist layer, and ultraviolet rays are irradiated through this mask. An exposure mask is developed and the resist layer is developed to obtain an etching mask for etching the metal film and metal base layer of the heat-resistant resin film with metal film. Next, the metal film and metal base layer exposed from the developed resist layer (the etching mask) are removed by etching, and the remaining resist layer (etching mask) is removed to obtain a wiring pattern It is. For the etching, an etchant such as a ferric chloride solution can be used.

  In the semi-additive method, a resist layer such as a dry film is provided on the surface of a metal film of a heat-resistant resin film with a metal film or a metal base layer of a heat-resistant resin film with a metal base layer, and a predetermined wiring pattern is formed on the resist layer. A mask for plating is provided for exposing the surface of the metal film or metal base layer to copper by electrodeposition and exposure by ultraviolet irradiation through the mask and developing the resist layer. Next, a wiring part is formed by electroplating using a metal film or metal base layer exposed from the developed resist layer (the plating mask) as a cathode, and then the remaining resist layer (the plating mask) Then, unnecessary metal film or metal base layer covered with the resist layer is removed by etching to obtain a wiring pattern. When obtaining a wiring pattern by a semi-additive method, it is possible to appropriately select whether to use a heat-resistant resin film with a metal base layer having a dielectric film or the heat-resistant resin film with a metal film. And when wiring pattern processing of the heat resistant resin film with a metal film is carried out by a semi-additive method, the thickness of the metal film should just be 1 micrometer or more, and it should just be the thickness which can be removed by etching.

  The wiring pattern is preferably formed on both sides of the flexible sheet by patterning both sides. Whether or not all the wiring patterns are divided into several wiring regions depends on the distribution of the wiring density of the wiring patterns. For example, the wiring pattern is divided into a high-density wiring area and a wiring area each having a wiring width and a wiring interval of 50 μm or less, and the wiring pattern is divided in consideration of the difference in thermal expansion from the printed circuit board and the handling convenience. What is necessary is just to divide suitably, setting a size to about 10-65 mm.

  As a method for forming the via hole, a conventionally known method can be used. For example, a via hole penetrating the wiring pattern and the flexible sheet is formed at a predetermined position of the wiring pattern by laser processing or the like. The diameter of the via hole is preferably reduced within a range that does not hinder the conductivity in the hole, and is usually 100 μm or less, preferably 50 μm or less. The via hole is filled with a conductive metal such as copper by plating, vapor deposition, sputtering, etc., or a conductive paste is pressed and dried using a mask having a predetermined opening pattern, and the inside of the hole is made conductive to form an interlayer. Make electrical connections.

  Examples of the present invention will be specifically described below.

  Using the apparatus 5 for producing a heat resistant resin film with a metal base layer having a dielectric film shown in FIG. 3, the long heat resistant resin film 8 has a width of 500 mm, a length of 200 m, and a thickness of 25 μm Ube Industries Ltd. A company-made heat-resistant polyimide film “UPILEX S (registered trademark)” was used.

  In addition, ion beam irradiation by introducing oxygen gas was applied to the surface treatment unit 13 in the first decompression chamber 7, and an ion beam voltage of 3 kV was applied.

In addition, the dielectric film formed by the ALD method uses Al ₂ O ₃ single atoms (monomolecules) for all three molecular layers, water molecules are introduced into the first reaction gas, and TMA [Trimethyl Aluminum: Al (CH ₃ ) ₃ ] gas was introduced. In each plasma reaction chamber 14, 15, 16, 17, 18, 19, 1 kW RF plasma is generated by introducing argon gas, and while the reaction gas is continuously introduced from the front of the first decompression chamber 7, Each vacuum chamber 7 was evacuated with an independent dry pump toward the back surface.

  The metal base layer was a Cu film, Cu was used for each magnetron sputtering target, argon gas was introduced at 300 sccm, and film formation was performed at each cathode power of 10 kW. The tension between the unwinding roll 9 and the winding roll 10 was 80N.

  And the said heat resistant polyimide film (heat resistant resin film) 8 is set to the unwinding roll 9 of the 1st decompression chamber 7, and surface treatment unit 13, each plasma reaction chamber 14-19, can roll 11, can roll 12, the tip of the heat-resistant polyimide film 8 was attached to the take-up roll 10.

In each of the second decompression chamber 6 for forming the sputtering method in the manufacturing apparatus 5 and the first decompression chamber 7 for depositing the ALD method, after evacuating to 5 Pa by a large dry pump, the sputtering method is further formed. The second decompression chamber 6 for performing the membrane was evacuated to 5 × 10 ⁻³ Pa using a turbo molecular pump and a cryocoil. The set value of the water cooling temperature control in each of the can rolls 11 and 12 was 20 ° C.

  And after making the conveyance speed of the said film (heat resistant polyimide film) 8 into 2 m / min, the ion beam of the surface treatment unit 13, the plasma of each plasma reaction chamber 14-19, and each magnetron sputtering cathode 20, 21, 22, Oxygen gas or argon gas was also introduced into 23, 24, 25, 26, and 27, and power was applied to the ion beam, plasma in each plasma reaction chamber, and each magnetron sputtering cathode to start film formation.

  At the time when the length of 190 m of the film 8 passed, the power to the ion beam, the plasma in each plasma reaction chamber and each magnetron sputtering cathode was stopped, and the introduction of each gas was also stopped.

  Finally, the conveyance of the film 8 is stopped and each pump is stopped, and then the second decompression chamber 6 and the first decompression chamber 7 are vented (open to the atmosphere), and the heat resistant polyimide film 8 of the unwinding roll 9 is removed. The end portion was removed, and all the films 8 were taken up on the take-up roll 10 and then removed.

Then, a part of the heat-resistant resin film with a metal base layer having the obtained dielectric film was cut out, and the first film formation surface (the Al ₂ O ₃ dielectric film formed on one surface of the film) Cu metal base layer) and the second film-forming surface (Al ₂ O ₃ dielectric film and Cu metal base layer formed on the other surface of the film) are partially etched only in the Cu metal base layer, and As a result of measuring the film thickness of Cu formed on each surface with a fluorescent X-ray film thickness meter, both the first film formation surface and the second film formation surface were about 100 nm.

  Thereafter, a metal film is formed on the metal base layer of the heat-resistant resin film with a metal base layer having a dielectric film by electrolytic plating until the total film thickness of Cu becomes 5 μm, and the metal film according to Example 1 A heat resistant resin film was obtained.

In the first embodiment, Al ₂ O _{3 is used} for the dielectric film. However, the dielectric film is selected from Si, Al, Zr, Hf, Ti, Ta, and Nb having oxygen permeation barrier other than Al ₂ O _3. It is also possible to employ at least one oxide film or nitride film.

  Example 1 except that a 7 wt% Cr—Ni alloy target was used as the sputtering target of the magnetron sputtering cathodes 20 and 27 in the apparatus 5 for producing a heat resistant resin film with a metal base layer having a dielectric film shown in FIG. In the same manner as described above, a heat resistant resin film with a metal base layer according to Example 2 was produced. That is, a heat-resistant resin film with a metal base layer in which a metal seed layer of 7 wt% Cr—Ni alloy was interposed between the dielectric film and the metal base layer was produced. The total film thickness of the Cr—Ni alloy metal seed layer and the Cu metal base layer was 100 nm as in Example 1.

[Comparative example]
As in the example, a heat resistant polyimide film “UPILEX S (registered trademark)” manufactured by Ube Industries, Ltd. having a width of 500 mm, a length of 200 m, and a thickness of 25 μm was used for the long heat resistant resin film 8.

  Further, in the comparative example, the dielectric film was not formed by the ALD method in the first decompression chamber 7, and the metal base layer was deposited by sputtering directly on the heat-resistant polyimide film surface in the second decompression chamber 6. . In addition, ion beam irradiation by introducing oxygen gas was applied to the surface treatment unit 13 in the first decompression chamber 7, and an ion beam voltage of 3 kV was applied.

  Moreover, the set value of the water cooling temperature control in each can roll was 20 degreeC. In addition, Cu was used for each magnetron sputtering target, 300 sccm of argon gas was introduced, and film formation was performed at each cathode power of 10 kW. The tension between the unwinding roll 9 and the winding roll 10 was 80N.

  And the said heat resistant polyimide film 8 is set to the unwinding roll 9 of the 1st decompression chamber 7, and it goes through the surface treatment unit 13, each plasma reaction chamber 14-19, the can roll 11, and the can roll 12 above. The tip of the heat-resistant polyimide film 8 was attached to the take-up roll 10.

About each of the 2nd decompression chamber 6 and the 1st decompression chamber 7 in the said manufacturing apparatus 5, after exhausting to 5 Pa with a large sized dry pump, the said 2nd decompression chamber 6 which forms the film of sputtering method is a turbo-molecular pump. It exhausted to 5 * 10 < ^-3 > Pa using the cryocoil.

  After the film transport speed is set to 2 m / min, oxygen gas or argon gas is also applied to the ion beam of the surface treatment unit 13 and each of the magnetron sputtering cathodes 20, 21, 22, 23, 24, 25, 26, 27. Introducing and applying power to the ion beam and each magnetron sputtering cathode to start the film forming process, and when the length of 190 m of the film 8 passes, the ion beam and power to each magnetron sputtering cathode And the introduction of each gas was also stopped.

  Finally, the conveyance of the film 8 is stopped and each pump is stopped, and then the second decompression chamber 6 and the first decompression chamber 7 are vented (open to the atmosphere), and the heat resistant polyimide film 8 of the unwinding roll 9 is removed. The end portion was removed, and all the films 8 were taken up on the take-up roll 10 and then removed.

  Then, a part of the heat-resistant resin film with a metal base layer according to the comparative example that does not include the dielectric film is cut out, and a first film formation surface (Cu metal base layer formed directly on one surface of the film) and The second film-forming surface (Cu metal base layer formed directly on the other surface of the film) is partially etched, and the film thickness of Cu formed on each surface is measured by a fluorescent X-ray film thickness meter. As a result of the measurement, both the first film formation surface and the second film formation surface were about 100 nm.

  Thereafter, a metal film was formed on the metal base layer of the heat-resistant resin film with a metal base layer according to the comparative example having no dielectric film until the total Cu film thickness became 5 μm by the electrolytic plating method. A heat-resistant resin film with a metal film according to the above was obtained.

"Evaluation"
Manufactured by forming a dielectric film (Al ₂ O ₃ ) by ALD on a heat resistant resin film and forming a metal base layer (Cu) by sputtering on this dielectric film (Al ₂ O ₃ ) A heat-resistant resin film with a metal base layer having a dielectric film according to Example 1, a dielectric film (Al ₂ O ₃ ) formed by an ALD method on the heat-resistant resin film as in Example 1, and A metal having a dielectric film according to Example 2 manufactured by forming a metal seed layer (Cr—Ni alloy) and a metal base layer (Cu) on the dielectric film (Al ₂ O ₃ ) by sputtering. A metal base layer (Cu) is formed by sputtering directly on the surface of the heat resistant resin film without forming a heat resistant resin film with a base layer and a dielectric film (Al ₂ O ₃ ) by ALD. Manufactured dielectric For the metal base layer with the heat-resistant resin film according to the comparative example having no film was subjected to adhesion measurement when left under the initial and high temperature and high humidity environment.

  That is, a heat resistant resin film with a metal film according to Examples 1 and 2 in which a metal film is formed by electrolytic plating on the heat resistant resin film with a metal base layer having a dielectric film according to Examples 1 and 2, and a dielectric A 100 mm square sample was cut out from each heat-resistant resin film with a metal film according to a comparative example in which a metal film was formed by electrolytic plating on the heat-resistant resin film with a metal base layer according to a comparative example without a body film, and etched. Thus, a 1 mm wide metal (Cu) stripe was formed on one side.

  And the adhesive force was measured about each sample of Examples 1-2 and the comparative example, respectively, peeling off the said metal stripe to a perpendicular direction. Furthermore, the samples of Examples 1 and 2 and the comparative example were left in an environmental tester at a temperature of 85 ° C. and a humidity of 85%, and the above-mentioned adhesion was measured every 100 hours. The results are shown in Table 1.

(1) From the data of the adhesion force (relative ratio) shown in Table 1, the heat resistant resin film with a metal base layer in Examples 1 and 2 having a dielectric film (Al ₂ O ₃ ) formed by the ALD method It was confirmed that the decrease in the adhesion strength in the environmental test was delayed as compared with the heat resistant resin film with a metal base layer according to the comparative example not having the dielectric film, and Example 1 and Example When the heat resistant resin film with a metal base layer according to 2 is compared, it is confirmed that the heat resistance resin film with a metal base layer according to Example 2 has a slower decrease in adhesion.

(2) The present inventor considers the reason why the above difference occurs as follows.

First, the heat-resistant resin film with a metal base layer in Examples 1 and 2 having a dielectric film (Al ₂ O ₃ ) formed by the ALD method is a pin formed by the ALD method although it has only three molecular layers. Oxygen supply from the heat-resistant resin film substrate is suppressed by the action of the dielectric film (Al ₂ O ₃ ) without holes, and it is considered that a decrease in adhesion due to oxidation of the metal base layer (Cu) can be prevented. And in the heat resistant resin film with a metal base layer according to Example 2, the effect of the metal seed layer (Cr—Ni alloy) was added together with the dielectric film (Al ₂ O ₃ ). It is considered that the lowering of the adhesion force was delayed more than the heat resistant resin film with a metal base layer. In addition, it can be expected that the above effect can be further increased by increasing the number of deposited molecular layers of the dielectric film (Al ₂ O ₃ ) by the ALD method.

(3) On the other hand, the heat resistant resin film with a metal base layer according to the comparative example not having the dielectric film (Al ₂ O ₃ ) is an oxidation of the metal base layer (Cu) by supplying oxygen from the heat resistant resin film substrate. It is considered that the adhesion is reduced due to the above.

  Therefore, it was confirmed that the decrease in the adhesion of the metal base layer (Cu) due to the oxygen supply from the heat resistant resin film substrate can be prevented by adopting the manufacturing method of the heat resistant resin film with metal base layer according to the present invention. Is done.

(4) In addition to the above adhesion strength measurement test, the heat-resistant resin film with metal base layer according to Examples 1 and 2 having a dielectric film (Al ₂ O ₃ ) and the comparative example not including the dielectric film A sample of 100 mm square was cut out from the heat resistant resin film with a metal base layer according to the above, and a test for measuring the number of pinholes having a diameter of 10 μm or more in the metal base layer formed on both surfaces of each sample was also performed. ing.

As a result, Examples 1-2 in which the metal base layer (Cu) was formed directly or via a metal seed layer (Cr—Ni alloy) on a dielectric film (Al ₂ O ₃ ) formed by the ALD method. In the heat resistant resin film with a metal base layer according to the present invention, the metal base layer (Cu) had no pinholes on both sides, whereas the heat resistance with a metal base layer according to a comparative example without the dielectric film In the resin film, it was confirmed that pinholes exist in the metal base layer (Cu).

  And this inventor thinks as a reason why a pinhole does not exist in a metal base layer (Cu) in the heat resistant resin film with a metal base layer which concerns on Examples 1-2.

That is, in the heat resistant resin films with metal base layers according to Examples 1 and 2, a dielectric film (Al ₂ O ₃ ) without a pinhole is formed on the surface along the heat resistant resin film surface by the ALD method. Since it is uniformly and uniformly formed by reaction, it is considered that pinholes are hardly formed in the metal base layer (Cu) formed by sputtering on the dielectric film (Al ₂ O ₃ ).

  According to the manufacturing method of the present invention, a heat resistant resin film with a metal base layer having a dielectric film that has excellent adhesion and no pinholes and prevents oxidation of the metal base layer can be continuously and efficiently manufactured. Therefore, the present invention has industrial applicability in which the heat-resistant resin film with a metal film obtained from the heat-resistant resin film with a metal base layer can be applied to flexible wiring such as liquid crystal televisions and mobile phones.

DESCRIPTION OF SYMBOLS 1 Heat resistant resin film 2 Dielectric film by ALD method 3 Metal base layer by sputtering method 4 Metal film by wet plating method 5 Manufacturing apparatus of heat resistant resin film with metal base layer having dielectric film 6 Second decompression chamber 7 First One decompression chamber 8 Heat-resistant resin film (heat-resistant polyimide film)
9 unwinding roll 10 winding roll 11 can roll 12 can roll 13 surface treatment unit 14 first reaction chamber 15 second reaction chamber 16 first reaction chamber 17 second reaction chamber 18 first reaction chamber 19 second reaction chamber 20 magnetron Sputter Cathode 21 Magnetron Sputter Cathode 22 Magnetron Sputter Cathode 23 Magnetron Sputter Cathode 24 Magnetron Sputter Cathode 25 Magnetron Sputter Cathode 26 Magnetron Sputter Cathode 27 Magnetron Sputter Cathode 28 Free Roll 29 Free Roll 30 Free Roll 31 Free Roll or Drive Roll 32 Free Roll or Drive Roll 33 Free roll 34 Free roll 35 Free roll 36 Free roll 37 Free roll or Drive roll 38 Roru or drive roll 39 free roll 40 free roll 41 partition wall 42 opening

Claims (10)

A dielectric film having a metal base layer formed by sputtering on each side of a long heat-resistant resin film and a metal film formed by wet plating on each metal base layer is provided. In the manufacturing method of the heat resistant resin film with a metal base layer having,
The long heat-resistant resin film unwound from the unwinding roll is transported by a roll-to-roll method and wound around the winding roll, and atomic layer deposition is performed on the transport path between the unwinding roll and the winding roll ( A first film forming step of forming dielectric films on both surfaces of the heat resistant resin film by an Atomic Layer Deposition (ALD) method;
A second film forming step of forming a metal base layer on one dielectric film by a first sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film is wound on the transport path;
A metal base layer is formed on the other dielectric film by a second sputtering web coater having a can roll and a sputter cathode around which a heat resistant resin film having a metal base layer formed on the one dielectric film is wound on the transport path. A third film forming step for forming a film;
A winding process in which a long heat-resistant resin film in which a metal base layer is formed on each dielectric film is wound on a winding roll;
And a process for producing a heat-resistant resin film with a metal base layer having a dielectric film, wherein the first film-forming process, the second film-forming process, and the third film-forming process are successively performed .   In the first film forming process, at least one or more pairs of first reaction chambers for introducing the first reaction gas and second reaction chambers for introducing the second reaction gas are alternately arranged in the conveyance direction of the heat resistant resin film. The method for producing a heat-resistant resin film with a metal base layer having a dielectric film according to claim 1, wherein the film is formed using a film forming means.   The dielectric film is composed of at least one oxide film or nitride film selected from Si, Al, Zr, Hf, Ti, Ta, and Nb, and the metal base layer is Cu or a Cu-based alloy. The method for producing a heat-resistant resin film with a metal base layer having a dielectric film according to claim 1, wherein the heat-resistant resin film has a dielectric film according to claim 1.   4. The metal seed layer selected from Ni or Ni alloy and formed by the sputtering web coater is interposed between the dielectric film and the metal base layer. A method for producing a heat-resistant resin film with a metal base layer having the dielectric film according to claim 1.   The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film, and has a heat resistance with a metal base layer having a dielectric film according to any one of claims 1 to 4. For producing a conductive resin film.   A metal film of the same type as the metal base layer by a wet plating method on each metal base layer of the heat-resistant resin film with a metal base layer having a dielectric film obtained by the production method according to claim 1. A method for producing a heat-resistant resin film with a metal film, wherein It has a dielectric film formed by atomic layer deposition (ALD) on both sides of a long heat-resistant resin film, and a metal base layer formed by sputtering on each dielectric film In the manufacturing equipment for heat resistant resin film with metal base layer,
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
In the first decompression chamber, an unwinding roll for unwinding the long heat-resistant resin film, a first reaction chamber for introducing the first reaction gas in the conveying direction of the unrolled heat-resistant resin film, and a second A means for forming a dielectric film in which at least one or more sets of second reaction chambers for introducing a reaction gas are alternately arranged; and
The second decompression chamber has a can roll and a sputter cathode around which the heat resistant resin film carried through the opening of the partition wall is wound, and a metal base layer on one dielectric film of the heat resistant resin film A first sputtering web coater for forming a film, a can roll having a heat-resistant resin film having a metal base layer formed on the one dielectric film and a sputtering cathode, and the other of the heat-resistant resin film A second sputtering web coater for forming a metal base layer on the dielectric film, and a winding roll for winding a long heat-resistant resin film in which the metal base layer is formed on each dielectric film are provided. As well as
A dielectric film characterized in that a plurality of roll groups constituting a roll-to-roll system conveying means are respectively provided in the first decompression chamber and the second decompression chamber in the conveyance direction of the heat resistant resin film An apparatus for producing a heat-resistant resin film with a metal base layer.   The dielectric film formed by the dielectric film forming means is composed of at least one oxide film or nitride film selected from Si, Al, Zr, Hf, Ti, Ta, Nb, and 8. The dielectric film according to claim 7, wherein the metal base layer formed by the first sputtering web coater and the second sputtering web coater is composed of one selected from Cu or a Cu-based alloy. Equipment for manufacturing heat-resistant resin film with metal base layer.   8. A metal seed layer selected from Ni or Ni alloy and interposed between the dielectric film and the metal base layer is formed by a first sputtering web coater and a second sputtering web coater, respectively. The manufacturing apparatus of the heat resistant resin film with a metal base layer which has a dielectric material film of description.   The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film, and has a heat resistance with a metal base layer having a dielectric film according to any one of claims 7 to 9. Equipment for conductive resin film.

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