JP5071428B2 - Manufacturing method of heat resistant resin film with metal base layer, heat resistant resin film with metal film and heat resistant resin film with metal base layer - Google Patents

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. A method for efficiently producing a heat-resistant resin film with a metal base layer having excellent adhesion and no pinholes, 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 a metal base The present invention relates to an apparatus for manufacturing a heat-resistant resin film with a layer.

  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 having excellent adhesion of the metal film. However, when carrying out this method, a metal base layer by sputtering and wet plating are used. It is important to set the thickness ratio of the metal film by the method. That is, the film thickness of the metal base layer formed by the sputtering method is required to be 200 nm or more in order 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 is 200 nm or more, even if a small pinhole exists, the pinhole of 10 μm or less is blocked with the growth of the metal base layer. . However, since the deposition rate of the metal base layer by sputtering is about an order of magnitude slower than the deposition rate of the wet plating method, heat resistance with a metal film is required because a metal base layer of 200 nm or more must be formed by sputtering. The production efficiency of the resin film will be deteriorated. Therefore, from the viewpoint of manufacturing efficiency, a new method that can form a metal base layer having no pinhole even if the film thickness is thinner than 200 nm has been desired.

Japanese Patent No. 3447070 Japanese Patent No. 3570802

Journal of applied physics 97,121301 (2005)

  The present invention has been made paying attention to such problems, and the object is to efficiently produce a heat-resistant resin film with a metal base layer having excellent adhesion to the metal base layer and no pinholes. It is providing the method, and also providing the manufacturing method of the heat resistant resin film with a metal film using this 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.

  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 by sputtering, a metal seed layer without pinholes is first formed on both surfaces of the heat-resistant resin film (deposition target) by ALD, and then on the metal seed layer by sputtering. It has been found that a metal base layer having no pinhole can be formed even when the thickness is less than 200 nm by forming a metal base layer on the substrate. The present invention has been completed by such technical discovery.

That is, the invention according to claim 1
Manufacture of heat-resistant resin films with metal base layers that have metal base layers formed by sputtering on both sides of a long heat-resistant resin film, and metal films are formed on each metal base layer by wet plating In the method
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 metal seed layers on both sides 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 metal seed layer 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 metal seed layer by a second sputtering web coater having a can roll and a sputter cathode on which a heat resistant resin film having a metal base layer formed on the one metal seed layer 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 metal seed layer 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 concerns on invention of Claim 1,
In the first film forming step, at least one or more pairs of first plasma reaction chambers for introducing the first reaction gas and second plasma reaction chambers for introducing the second reaction gas are alternately arranged in the conveyance direction of the heat resistant resin film. It is characterized in that it is performed using a film forming means of the metal seed layer,
The invention according to claim 3
In the manufacturing method of the heat resistant resin film with a metal base layer which concerns on invention of Claim 1 or 2,
The metal seed layer is composed of one kind selected from Ni, Ni-based alloy, Cu and Cu-based alloy, and the metal base layer is composed of one kind selected from Cu or Cu-based alloy. As a feature,
The invention according to claim 4
In the manufacturing method of the heat resistant resin film with a metal base layer which concerns on the invention in any one of Claims 1-3,
The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film.

The invention according to claim 5
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 is formed on each metal base layer of the heat-resistant resin film with a metal base layer obtained by the manufacturing method according to claim 1 by a wet plating method. It is characterized by.

Next, the invention according to claim 6 is:
A metal seed layer formed by atomic layer deposition (ALD) on each side of a long heat-resistant resin film, and a metal base layer formed by sputtering on each metal seed layer; In the manufacturing apparatus of the heat resistant resin film with a metal base layer having
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 a long heat-resistant resin film, a first plasma reaction chamber for introducing a first reaction gas in the transport direction of the unrolled heat-resistant resin film, and a first A metal seed layer forming means in which at least one pair of second plasma reaction chambers for introducing two reaction gases 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 metal seed layer 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 metal seed layer 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 metal seed layer and a take-up roll for winding a long heat-resistant resin film in which the metal base layer is formed on each metal seed layer 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 7 provides:
In the manufacturing apparatus of the heat resistant resin film with a metal base layer which concerns on invention of Claim 6,
The metal seed layer formed by the metal seed layer forming means is composed of one selected from Ni, Ni-based alloy, Cu, and Cu-based alloy, and the first sputtering web coater and the second sputtering web coater. The metal base layer formed by is composed of one kind selected from Cu or Cu-based alloys,
The invention according to claim 8 is
In the manufacturing apparatus of the heat resistant resin film with a metal base layer which concerns on invention of Claim 6 or 7,
The long heat-resistant resin film is composed of one kind selected from a polyimide film or an aramid film.

The manufacturing method of the heat resistant resin film with a metal base layer which concerns on Claims 1-4 is as follows.
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 metal seed layers on both sides 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 metal seed layer 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 metal seed layer by a second sputtering web coater having a can roll and a sputter cathode on which a heat resistant resin film having a metal base layer formed on the one metal seed layer 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 metal seed layer 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 metal seed layer without a pinhole 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 film thickness of the metal base layer formed on each metal seed layer does not need to be set to a size that closes the pinhole as in the conventional method.

  Therefore, since the thickness of each metal base layer can be set thinner than that of the conventional method, it is possible to efficiently produce a heat resistant resin film with a metal base layer that is excellent in adhesion of the metal base layer and has no pinholes.

Moreover, the manufacturing method of the heat resistant resin film with a metal film which concerns on Claim 5 is as follows.
A metal film of the same type as the metal base layer is formed on each metal base layer of the heat-resistant resin film with a metal base layer obtained by the manufacturing method according to claim 1 by a wet plating method. Therefore, the heat resistant resin film with a metal film can be efficiently manufactured by the amount that the heat resistant resin film with a metal base layer can be efficiently manufactured.

Next, the manufacturing apparatus of the heat resistant resin film with a metal base layer which concerns on Claims 6-8 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 a long heat-resistant resin film, a first plasma reaction chamber for introducing a first reaction gas in the transport direction of the unrolled heat-resistant resin film, and a first A metal seed layer forming means in which at least one pair of second plasma reaction chambers for introducing two reaction gases 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 metal seed layer 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 metal seed layer 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 metal seed layer and a take-up roll for winding a long heat-resistant resin film in which the metal base layer is formed on each metal seed layer are provided. As well as
A plurality of groups of rolls constituting a roll-to-roll type conveying means are provided in the first decompression chamber and the second decompression chamber over the conveyance direction of the heat-resistant resin film. Thus, it is possible to efficiently and reliably produce a heat resistant resin film with a metal base layer that has excellent adhesion to the metal base layer and has no pinholes.

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 concerns on this invention.

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

  First, the heat resistant resin film with a metal film according to the present invention is formed by an atomic layer deposition (ALD) method on both surfaces of the heat resistant resin film 1 and the heat resistant resin film 1 as shown in FIG. Metal seed layer 2, metal base layer 3 formed on each metal seed layer 2 by a sputtering method, and metal film 4 formed on each metal base layer 3 by a wet plating method. Yes.

  Further, a precursor before the metal film 4 is formed, that is, a heat-resistant resin film 1, a metal seed layer 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 metal seed layer 2 is the heat resistant resin film with a metal base layer according to the present invention.

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

  Further, in the film formation by the atomic layer deposition (ALD) method in the first film formation step, 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. In addition, since it is a method of depositing single atom (monomolecular) layers one by one, as described above, pinholes can be formed even in minute gaps without being affected by irregularities on the surface of the heat resistant resin film 1 (film formation target). No thin film can be formed.

  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.

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 a non-metal film (metal seed layer). 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 I 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. Excess second reaction gas and by-products are exhausted from the vacuum apparatus. And, in the ALD method, oxide films such as SiO ₂ , Al ₂ O ₅ , ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , TiO ₂ , AlN, Nitride films such as TaN, TiN, TaSiN, TiSiN, metal films such as Cu, Ru, Ir, Ni, Pt, fluoride films such as CaF ₂ , SrF ₂ , MgF ₂ , compound films such as GaAs, InP, and 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.

In the method for producing a heat-resistant resin film with a metal base layer according to the present invention, Cu as a metal seed layer is formed by ALD, so that CuCl ₂ , Cu (acac) ₂ , Cu (thd) ₂ , Cu (hfac) ₂ ) is preferably used as the reaction gas. Of these, Cu (thd) ₂ is preferably used. When Cu (thd) ₂ is used, H ₂ is combined with one reaction gas.

In the method for producing a heat resistant resin film with a metal base layer according to the present invention, it is preferable to use Ni (acac) ₂ as a reaction gas in order to form Ni as a metal seed layer by the ALD method. When Ni (acac) ₂ is used as a reaction gas, one reaction gas is combined with H ₂ .

Here, the above (acac), (thd), and (hfac) mean the following.
(Acac) = 2,4-pentanedionate
(Thd) = 2,2,6,6-tetramethyl-3,5-heptanedionate
(Hfac) = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate

2. Sputtering web coater The heat-resistant resin film with a metal film of the present invention comprises a heat-resistant resin film 1 and a metal film formed by atomic layer deposition (ALD) on both surfaces of the heat-resistant resin film 1 as shown in FIG. The seed layer 2 includes a metal base layer 3 formed on each metal seed layer 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 this invention, the sputtering web coater which can form a metal film efficiently on a long film surface as a means to form the metal base layer 3 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 sputter 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 metal seed layer is formed is wound around the can roll, thermal damage of the heat-resistant resin film due to plasma during 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 sputtering film formation of the metal base layer 3, but when a plate-like target is used, nodules (growth of foreign matter) 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 equipment for heat-resistant resin film with metal base layer Metal seed layer formed on both sides of long heat-resistant resin film by atomic layer deposition (ALD) method, and film formation on each metal seed layer by sputtering method An apparatus for producing a heat-resistant resin film with a metal base layer according to the present invention having a metal base layer formed is provided with a first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition wall And a first plasma that introduces a first reactive gas across the unwinding roll for unwinding the long heat-resistant resin film and the conveying direction of the unrolled heat-resistant resin film. A metal seed layer forming means in which at least one set of reaction chambers and second plasma reaction chambers for introducing the second reaction gas are alternately arranged is provided, and an opening portion of a partition wall is provided in the second decompression chamber. Through A first sputtering web coater having a can roll and a sputtering cathode around which the heat-resistant resin film to be carried is wound and forming a metal base layer on one metal seed layer of the heat-resistant resin film, and the one metal A second sputtering web having a can roll on which a heat resistant resin film having a metal base layer formed on a seed layer is wound and a sputtering cathode, and forming a metal base layer on the other metal seed layer of the heat resistant resin film A coater and a take-up roll for winding a long heat-resistant resin film in which a metal base layer is formed on each metal seed layer are provided, and a roll-to-roll type conveying means is configured. A plurality of roll groups 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 metal seed layer 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. Thus, the first plasma reaction chamber for introducing the first reaction gas and the second plasma 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, at least one set of the first plasma reaction chamber for introducing the first reaction gas and the second plasma reaction chamber for introducing the second reaction gas are alternately arranged. By passing the heat-resistant resin film through the chamber region, a metal seed layer is formed while each reaction of the ALD method described above is performed in each plasma reaction chamber.

  In the manufacturing apparatus according to the present invention, the first decompression chamber in which the metal seed layer is deposited by the ALD method and the second decompression chamber in which the metal base layer is deposited by the sputtering method are suitable for deposition. Since the gas pressures are different, it is necessary to partition each decompression chamber with the partition wall and maintain a gas pressure suitable for each film formation by differential evacuation. 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. 2, the manufacturing apparatus 5 for a heat resistant resin film with a metal base layer according to the present invention includes a first decompression chamber 7 in which a metal seed layer is formed by the ALD method, and an opening 42. And a second decompression chamber 6 in which a metal base layer is formed by a sputtering method provided adjacent to the partition wall 41 through the partition wall 41 having the partition wall 41. Further, the gas pressure suitable for film formation differs between the first decompression chamber 7 where the metal seed layer is formed by the ALD method and the second decompression chamber 6 where the metal base layer is formed by the sputtering method. 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 pairs of first plasma reaction chambers and second plasma reaction chambers for introducing the second reaction gas are alternately arranged (that is, first plasma reaction chambers 14, 16, 18 and second plasma reaction chambers 15, 17, 19). In addition, the heat-resistant resin film 8 carried through the opening 42 of the partition wall 41 is wound in the second decompression chamber 6 and the water roll temperature-controlled can roll 11 and four magnetrons are wound. A first sputtering web coater having sputter cathodes 20, 21, 22, 23 and forming a metal base layer on one metal seed layer of the heat-resistant resin film 8, and a metal on the one metal seed layer. The other metal of the heat-resistant resin film 8 has a can roll 12 wound with a heat-resistant resin film on which a glass layer is wound and water-cooled and temperature-controlled, and four magnetron sputter cathodes 24, 25, 26 and 27. A second sputtering web coater for forming a metal base layer on the seed layer, and a take-up roll 10 for winding the long heat-resistant resin film 8 having the metal base layer formed on each metal seed layer. Furthermore, a plurality of free rolls 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 constituting a roll-to-roll type conveying means are heat resistant. The first decompression chamber 7 and the second decompression chamber 6 are provided in the transport direction of the conductive resin film 8, 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.

  It is also possible to dispose a surface treatment unit 13 for performing plasma treatment or ion beam treatment introducing argon gas, oxygen gas, or the like, at a position before the film formation by the ALD method in the first decompression chamber 7. is there. By disposing such a surface treatment unit 13, both surfaces of the heat resistant resin film 8 can be cleaned and activated.

  The heat-resistant resin film 8 whose both surfaces are cleaned and activated by the surface treatment unit 13 includes the first plasma reaction chamber 14 into which the first reaction gas is introduced and the second plasma into which the second reaction gas is introduced. A reaction chamber 15, a first plasma reaction chamber 16 introduced with a first reaction gas, a second plasma reaction chamber 17 introduced with a second reaction gas, a first plasma reaction chamber 18 introduced with a first reaction gas, and By passing through the second plasma reaction chamber 19 into which the second reaction gas has been introduced, the above-described reaction by the ALD method occurs, and a metal seed layer of three atoms (molecules) is formed on both surfaces. In order to increase the atomic layer of the metal seed layer, the first plasma chamber into which the first reaction gas is introduced and the second plasma chamber into which the second reaction gas is introduced may be added. In addition, by selecting the reaction gas, it is possible to make the triatomic layer a metal seed layer of Cu or Ni alone, or make only the first layer a Ni metal seed layer and the second and third layers. The layer can also be a Cu metal seed layer.

  Next, the heat-resistant resin film 8 having the metal seed layer formed on both surfaces was carried from the first decompression chamber 7 through the opening 42 of the partition wall 41 into the second decompression chamber 6 and adjusted to water cooling temperature. 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 film was wound on a can roll 11 that was temperature-cooled using four magnetron sputter cathodes 20, 21, 22, and 23 to which a metal target for forming a metal base layer was attached. Four magnetron sputter cathodes 24 having a metal base layer formed on the first film formation surface (on one metal seed layer) of the heat-resistant resin film 8 and further having a metal target for forming the metal base layer attached thereto, After the metal base layer is formed on the second film formation surface (on the other metal seed layer) of the heat-resistant resin film 8 wound on the can roll 12 that is temperature-cooled using 25, 26, and 27 The heat-resistant resin film 8 having a metal base layer formed on each metal seed layer is wound around a take-up roll 10 and the metal base according to the present invention. With heat-resistant resin film is obtained.

  When a metal film is formed on the metal base layer of the obtained heat-resistant resin film with a metal base layer using a wet plating method, the electroplating process is performed alone, or the electroless plating process is performed as the primary plating. In some cases, wet plating such as electrolytic plating is combined as the next plating. The wet plating process may employ various conditions of a conventional wet plating method.

  Furthermore, a metal film is further formed by a wet plating method on the metal base layer formed on the metal seed layer where there is no pinhole even with a thin film thickness, thereby satisfying the advantages of both adhesion and manufacturing cost. It becomes possible to obtain the heat-resistant resin film with a metal film. In addition, the total thickness of the metal layers (the metal base layer and the metal film) formed by the dry (sputtering method) and the wet plating method formed on the metal seed layer in this way should be at most 18 μm or less. Is preferred.

  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.

  As a method for forming the wiring pattern, a conventionally known method such as photoetching can be used. For example, a heat-resistant resin film with a metal film is prepared, and a screen printing or dry film is laminated on the metal film to make it photosensitive. After forming the resist film, exposure and development are performed for patterning. Next, the metal film is selectively removed by etching with an etchant such as a ferric chloride solution, and then the resist film is removed to form a predetermined wiring pattern. It is preferable to form a wiring pattern on both surfaces of the flexible sheet by patterning both surfaces. 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 heat-resistant resin film manufacturing apparatus 5 with the metal base layer shown in FIG. 2, the long heat-resistant resin film 8 has a heat resistance of Ube Industries, Ltd. having a width of 500 mm, a length of 200 m, and a thickness of 25 μm. A 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.

Moreover, the metal seed layer by ALD method made all the atomic layers into Cu, introduced hydrogen gas into the first reaction gas, and introduced Cu (thd) ₂ into the second reaction gas. 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 of the decompression chamber 7.

  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 sputter 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 sputter cathode to start film formation.

  Then, 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 the 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 obtained heat-resistant resin film with a metal base layer is cut out, and a first film-forming surface (a Cu metal seed layer and a metal base layer formed on one surface of the film) and a second component are formed. The film surface (Cu metal seed layer and metal base layer formed 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 measurement, the first film formation surface and the second film formation surface were both 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 by electrolytic plating until the film thickness of the entire Cu becomes 5 μm, and the heat resistant resin film with a metal film according to the example is obtained. Obtained.
[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.

  In the comparative example, the metal seed layer was not formed by the ALD method in the first decompression chamber 7, and the metal base layer was formed 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 sputter cathodes 20, 21, 22, 23, 24, 25, 26, 27. Introduced and applied power to the ion beam and each magnetron sputter cathode to start the film forming process, and when the film 8 has passed the length of 190 m, the power to the ion beam and each magnetron sputter 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 obtained heat-resistant resin film with a metal base layer according to the comparative example was cut out, and the first film-formed surface (Cu metal base layer formed directly on one surface of the film) and the second The film-forming surface (Cu metal base layer directly formed on the other surface of the film) is partially etched, and the film thickness of Cu formed on each surface is measured with a fluorescent X-ray film thickness meter. As a result, the first film formation surface and the second film formation surface were both 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 according to the comparative example until the total film thickness of Cu becomes 5 μm by electrolytic plating, and the heat resistance with the metal film according to the comparative example is achieved. A functional resin film was obtained.

"Evaluation"
According to an embodiment manufactured by forming a metal seed layer (Cu) by ALD method on a heat resistant resin film and forming a metal base layer (Cu) by sputtering method on the metal seed layer (Cu) It is manufactured by forming a metal base layer (Cu) directly on the surface of the heat resistant resin film without forming the metal seed layer (Cu) by the ALD method and the heat resistant resin film with the metal base layer. For the heat resistant resin film with metal base layer according to the comparative example, the number of pinholes present in each metal base layer was measured.

  That is, 100 mm square samples were cut out from the heat resistant resin film with metal base layer according to the example and the heat resistant resin film with metal base layer according to the comparative example, and the diameter in the metal base layer formed on both surfaces of each sample. The number of pinholes of 10 μm or more was measured by microscopic observation.

  As a result, the metal base layer (Cu) according to the example in which the metal base layer (Cu) was formed on the metal seed layer (Cu) by the ALD method had no pinholes on both sides. On the other hand, the metal base layer (Cu) according to the comparative example formed by sputtering directly on the surface of the heat-resistant resin film without forming the metal seed layer (Cu) by the ALD method has pinholes, Twenty-six pinholes were measured in the metal base layer (Cu) on the first film formation surface, and 36 pinholes were measured in the metal base layer (Cu) on the other second film formation surface.

  The present inventor considers the reason why such a difference occurs as follows.

  First, in the heat resistant resin film with a metal base layer according to the example, a metal seed layer (Cu) having no pinholes on both surfaces of the heat resistant resin film is formed on the surface along the surface of the heat resistant resin film by the ALD method. Since it is uniformly and uniformly formed by a chemical reaction, it is considered that pinholes are hardly formed in the metal base layer (Cu) formed by sputtering on the metal seed layer (Cu) that is a metal surface.

  On the other hand, in the heat resistant resin film with a metal base layer according to the comparative example, the metal seed layer (Cu) by the ALD method is not formed, and the metal base layer (Cu) is directly formed on the surface of the heat resistant resin film by the sputtering method. Since it is formed into a film (that is, particles that fly from the target due to the sputtering phenomenon are deposited on the heat-resistant resin film), it is affected by scratches existing on the surface of the heat-resistant resin film, This is considered to be because pinholes are likely to occur at the interface between the heat-resistant resin film and the metal base layer (Cu), and the pinholes cannot be blocked by the thickness of the metal base layer (Cu) having a thickness of about 100 nm.

  According to the manufacturing method of the present invention, since there are no pinholes in the metal seed layer formed on both surfaces of the heat-resistant resin film by the ALD method, the film is formed on the metal seed layer by the sputtering method. Since pinholes are hardly generated in the metal base layer, the thickness of the metal base layer can be set as thin as it is not necessary to close the pinholes.

  Therefore, it can be confirmed that the heat-resistant resin film with a metal base layer having excellent adhesion to the metal base layer and having no pinholes can be efficiently produced as much as the film thickness of the metal base layer can be set thinner than the conventional method.

  According to the production method of the present invention, a heat-resistant resin film with a metal base layer that is excellent in adhesion of the metal base layer and has no pinholes can be efficiently produced. The present invention has industrial applicability in which a heat-resistant resin film with a metal film can be applied to flexible wiring such as liquid crystal televisions and mobile phones.

DESCRIPTION OF SYMBOLS 1 Heat resistant resin film 2 Metal seed layer 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 6 Second decompression chamber 7 First decompression chamber 8 Heat resistance Resin film (heat-resistant polyimide film)
DESCRIPTION OF SYMBOLS 9 Unwinding roll 10 Winding roll 11 Can roll 12 Can roll 13 Surface treatment unit 14 1st plasma reaction chamber 15 2nd plasma reaction chamber 16 1st plasma reaction chamber 17 2nd plasma reaction chamber 18 1st plasma reaction chamber 19 1st 2 Plasma reaction chamber 20 Magnetron sputtering cathode 21 Magnetron sputtering cathode 22 Magnetron sputtering cathode 23 Magnetron sputtering cathode 24 Magnetron sputtering cathode 25 Magnetron sputtering cathode 26 Magnetron sputtering cathode 27 Magnetron sputtering 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 free roll or drive roll 39 free roll 40 free roll 41 partition wall 42 opening

Claims (8)

Manufacture of heat-resistant resin films with metal base layers that have metal base layers formed by sputtering on both sides of a long heat-resistant resin film, and metal films are formed on each metal base layer by wet plating In the method
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 metal seed layers on both sides 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 metal seed layer 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 metal seed layer by a second sputtering web coater having a can roll and a sputter cathode on which a heat resistant resin film having a metal base layer formed on the one metal seed layer 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 metal seed layer is wound on a winding roll;
And a process for producing a heat-resistant resin film with a metal base layer, 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 step, at least one or more pairs of first plasma reaction chambers for introducing the first reaction gas and second plasma 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 according to claim 1, wherein the metal seed layer is formed using the film forming means.   The metal seed layer is composed of one kind selected from Ni, Ni-based alloy, Cu and Cu-based alloy, and the metal base layer is composed of one kind selected from Cu or Cu-based alloy. The manufacturing method of the heat resistant resin film with a metal base layer of Claim 1 or 2 characterized by the above-mentioned.   The said long heat resistant resin film is comprised by 1 type chosen from a polyimide film or an aramid film, The manufacture of the heat resistant resin film with a metal base layer in any one of Claims 1-3 characterized by the above-mentioned. Method.   A metal film of the same type as the metal base layer is formed on each metal base layer of the heat-resistant resin film with a metal base layer obtained by the manufacturing method according to claim 1 by a wet plating method. The manufacturing method of the heat resistant resin film with a metal film characterized by these. A metal seed layer formed by atomic layer deposition (ALD) on each side of a long heat-resistant resin film, and a metal base layer formed by sputtering on each metal seed layer; In the manufacturing apparatus of the heat resistant resin film with a metal base layer having
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 a long heat-resistant resin film, a first plasma reaction chamber for introducing a first reaction gas in the transport direction of the unrolled heat-resistant resin film, and a first A metal seed layer forming means in which at least one pair of second plasma reaction chambers for introducing two reaction gases 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 metal seed layer 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 metal seed layer 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 metal seed layer and a take-up roll for winding a long heat-resistant resin film in which the metal base layer is formed on each metal seed layer are provided. As well as
A metal base layer 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 over the conveyance direction of the heat-resistant resin film Heat-resistant resin film manufacturing equipment.   The metal seed layer formed by the metal seed layer forming means is composed of one selected from Ni, Ni-based alloy, Cu, and Cu-based alloy, and the first sputtering web coater and the second sputtering web coater. 7. The apparatus for producing a heat-resistant resin film with a metal base layer according to claim 6, wherein the metal base layer formed by 1 is composed of one selected from Cu or a Cu-based alloy.   The said long heat resistant resin film is comprised by 1 type chosen from a polyimide film or an aramid film, The manufacturing apparatus of the heat resistant resin film with a metal base layer of Claim 6 or 7 characterized by the above-mentioned.

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