JP2015081373A - Method and device for double side film deposition, and production method of resin film with metal base layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for double side film deposition, which prevents blocking phenomena that metal films stick together, when a long body is rolled in immediately after metal films are deposited on both faces.SOLUTION: The method for double side deposition, which deposits a metal film on both sides of a long body transported by roll-to-roll in low pressure atmosphere, includes: a first deposition step of depositing a metal film on one face of the long body by a first sputtering means; a second deposition step of depositing a metal film on the other face of the long body by a second sputtering means; and a third deposition step of forming a blocking prevention layer composed of a metal oxide film or a metal nitride film on the metal film by an atomic layer deposition (ALD) method; and a rolling step of rolling the long body on which the blocking prevention layer is formed, and rolling it in a take-up reel. The first deposition step, the second deposition step and the third deposition step are contiguously performed.

Description

  The present invention relates to a double-sided film formation method and apparatus for continuously forming a metal film on both surfaces of a long body such as a long resin film by sputtering, and particularly immediately after the metal film is formed on both sides. It is related with the improvement of the double-sided film-forming method and double-sided film-forming apparatus which are hard to produce the blocking phenomenon in which metal films adhere when a long resin film (long body) is wound on a take-up roll.

  For liquid crystal panels, notebook computers, digital cameras, mobile phones, etc., many types of flexible wiring boards obtained by coating a metal film on a resin film are used. This flexible wiring board has metal on both sides of the resin film. A resin film with a metal film in which a film is formed is used. In addition, since the resin film with a metal film may be used by being bent, the metal film needs to have high adhesion to the resin film. Since pinholes are likely to cause disconnection, there is also a need for no pinholes.

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

  Moreover, as a third manufacturing method using a vacuum film forming method or a wet plating method, a method of manufacturing a resin film with a metal film using a sputtering method capable of forming a metal film having a low film forming speed but excellent adhesion is disclosed. A thin film metal base layer is first formed using a sputtering method disclosed in Document 1 and capable of forming a metal film having a low film formation speed but excellent adhesion, and then a wet plating method having a high film formation speed is used. Patent Document 2 discloses a method for efficiently producing a resin film with a metal film by forming a thick metal film on the metal base layer. 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.

  A sputtering web coater is widely used as an apparatus for efficiently forming a metal film on both sides of a long resin film (long body) by sputtering, and Patent Document 4 and Patent Document 5 disclose a sputtering web coater. An example is disclosed.

  By the way, when a metal film is formed on both sides of a long resin film (long body) using a sputtering web coater, the metal film immediately after the film formation has a high surface activity. For this reason, when a long resin film immediately after a metal film is formed on both sides is wound on a take-up roll, a phenomenon called blocking in which the metal films adhere to each other may occur. In some cases, the metal film formed on one surface of the long resin film peels off and sticks to the other surface, or a film wrinkle is generated. In consideration of the mechanism of the blocking phenomenon, if a long resin film (long body) on which a metal film is formed is wound under atmospheric pressure, a gas is generated between the metal films of the long resin film. Because of being caught, the blocking phenomenon is less likely to occur. However, the inside of the sputtering web coater in operation is under a reduced pressure atmosphere, and there is no gas that is caught between the metal films of the long resin film, so that the blocking phenomenon occurs.

  As a method for solving this problem, Patent Document 3 proposes a method of applying an organic liquid such as vacuum pump oil to the surface of a metal film immediately after film formation. However, the method proposed in Patent Document 3 has a problem that an organic liquid such as vacuum pump oil must be removed, and the organic liquid needs to be handled in a sputtering web coater under a reduced pressure atmosphere. There was a problem that the frequency of maintenance increased.

  Patent Document 4 proposes a method for preventing the blocking by forming an oxide film by performing ion beam irradiation treatment or plasma treatment on the surface of the metal film immediately after the film formation. However, in the method proposed in Patent Document 4, the inside of the film forming apparatus may be contaminated due to the sputtering action of the metal film when irradiated with an ion beam or the like, and the maintenance frequency may increase accordingly. There is concern about sex.

  In Patent Document 5, a metal film is formed on both surfaces of a long resin film (long body) using a sputtering web coater, and a metal oxide thin film is continuously formed on the surface of the metal film by a sputtering web coater. A method for preventing blocking by forming a film is proposed. However, in the method proposed in Patent Document 5, when the metal oxide thin film is continuously formed on the surface of the metal film by the sputtering web coater, if the metal oxide thin film is too thin, the presence of pinholes, etc. Concerns about the occurrence of blocking, on the contrary, if the film thickness is too thick, etching treatment of the metal oxide thin film (when applying a long resin film with a metal film formed on both sides as a resin film with a metal base layer, There is a concern that the metal oxide thin film needs to be removed before the thick metal film is formed on the metal base layer by the wet plating method.

Japanese Patent No. 3447070 (see claims) Japanese Patent No. 3570802 (refer to claims) JP 2009-249703 A (refer to claims) JP 2010-053447 A (refer to claims) JP 2012-246511 A (see claims)

Journal oF applied physics 97,121301 (2005)

  The present invention has been made paying attention to such problems, and the problem is that when the long body immediately after the metal film is formed on both sides is wound on the take-up roll, the metal film An object of the present invention is to provide a double-sided film forming method and a double-sided film forming apparatus in which the blocking phenomenon of sticking to each other hardly occurs, and to provide a method for producing a resin film with a metal base layer using the double-sided film forming method.

  In order to solve the above problems, the present inventor described in Non-Patent Document 1 instead of the method of Patent Document 5 in which a metal oxide thin film is continuously formed on the surface of the metal film using a sputtering web coater. An attempt was made to adopt an atomic layer deposition (ALD) method. 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). The film formation speed is slower than the sputtering method using a sputtering web coater, but from the target as in the sputtering method. Because it is not a method of depositing and stacking the fine particles and clusters on the film formation body, it can form a very thin film without pinholes and without being affected by the unevenness of the surface of the film formation body. An extremely thin film can be formed even in a minute gap.

  Therefore, the present inventor has formed a metal film on both surfaces of a long body such as a long resin film, and then used the above ALD method to form a metal oxide that is extremely thin (several atomic layers or less) and has no pinholes. When a film or a metal nitride film is formed, it has been found that blocking is reduced.

  In addition, a long resin film (long body) in which a metal oxide film or metal nitride film that is extremely thin (less than several atomic layers) and has no pinholes is formed on the surface of the metal film is provided with the above-described metal base layer. When applied as a resin film (that is, adopting the method described in Patent Document 2 in which a sputtering method having a low film formation rate and a wet plating method having a high film formation rate are used together), it is extremely thin (several atomic layers) by a slight etching process. And a metal oxide film or metal nitride film having no pinholes can be removed, so that the wet plating process is not adversely affected.

  The present invention has been completed by such technical discovery.

That is, the invention according to claim 1
In a double-sided film forming method for forming a metal film on both sides of a long body conveyed by a roll-to-roll under a reduced pressure atmosphere,
A first film forming step of forming a metal film on one surface of the long body by a first sputtering means having a can roll and a sputter cathode provided on the conveying path of the long body;
A second film forming step of forming a metal film on the other surface of the elongated body by a second sputtering means having a can roll and a sputter cathode provided on a downstream conveyance path of the first sputtering means;
A third composition in which a metal oxide film or a metal nitride film is formed by atomic layer deposition (ALD) on at least one metal film of the elongated body on the downstream transport path of the second sputtering means. A membrane process;
A winding step of winding a long body on which a metal oxide film or a metal nitride film is formed, 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 double-sided film-forming method according to claim 1,
The metal oxide film or metal nitride film formed in the third film forming step is at least one metal oxide film or metal nitride selected from Ti, Zn, Ce, Ni, Sn, Si, Al, and Cu. It is a material film,
The invention according to claim 3
In the double-sided film-forming method according to claim 1 or 2,
The long body is composed of one kind selected from a polyimide film, an aramid film, a liquid crystal polymer, and a polytetrafluoroethylene film.

Next, the invention according to claim 4 is:
A metal film is formed on one surface of the long body by the first sputtering means, a metal film is formed on the other surface of the long body by the second sputtering means, and at least one of the above metals of the long body In a double-sided film forming apparatus for forming a metal oxide film or a metal nitride film on the film by an atomic layer deposition (ALD) method,
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
The first decompression chamber has an unwinding roll for unwinding the long body, a can roll and a sputter cathode around which the long body unwound from the unwinding roll is wound, and one of the long bodies A first sputtering web coater for forming a metal film on the surface, a can roll and a sputter cathode around which the long body having the metal film formed by the first sputtering web coater is wound; A second sputtering web coater for forming a metal film on the other surface is provided; and
In the second decompression chamber, a first plasma reaction chamber for introducing the first reaction gas and a second plasma reaction for introducing the second reaction gas are introduced in the conveying direction of the elongated body carried in through the opening of the partition wall. Forming means for metal oxide film or metal nitride film in which at least one set of chambers are alternately arranged, and a winding roll for winding up the long body on which the metal oxide film or metal nitride film is formed Is provided,
A plurality of roll groups constituting a roll-to-roll conveyance means are provided in the first decompression chamber and the second decompression chamber, respectively, in the conveyance direction of the long body.

Furthermore, the invention according to claim 5
The long body is composed of a long resin film, and the metal film formed on both sides of the long body is composed of a metal seed layer and a metal base layer formed on the metal seed layer. In the manufacturing method of the resin film with a metal base layer,
The double-sided film forming method according to any one of claims 1 to 3, wherein the metal seed layer is made of a Ni alloy, the metal base layer is made of Cu or a Cu alloy, and the metal seed layer and the metal base layer are formed. The film is formed by the above.

The method for producing a resin film with a metal base layer according to claim 5 using the double-sided film forming method according to claims 1 to 3 and the double-sided film forming method,
A first film forming step of forming a metal film on one surface of the long body by a first sputtering means having a can roll and a sputter cathode provided on the conveying path of the long body;
A second film forming step of forming a metal film on the other surface of the elongated body by a second sputtering means having a can roll and a sputter cathode provided on a downstream conveyance path of the first sputtering means;
A third composition in which a metal oxide film or a metal nitride film is formed by atomic layer deposition (ALD) on at least one metal film of the elongated body on the downstream transport path of the second sputtering means. A membrane process;
A winding step of winding a long body on which a metal oxide film or a metal nitride film is formed, on a winding roll;
And the first film-forming process, the second film-forming process, and the third film-forming process are continuously performed.

  In the third film forming step, a metal oxide film or metal nitride film without a pinhole is formed on at least one of the long metal films formed on both surfaces of the metal film. The above-described blocking phenomenon can be reliably prevented, and the metal oxide film or metal nitride film formed by the ALD method is an extremely thin film (several atomic layers or less) that can be removed by a slight etching process. Therefore, when a long body having a metal film formed on both surfaces is applied as a resin film with a metal base layer, the wet plating process is not adversely affected.

Next, a double-sided film forming apparatus according to claim 4 is:
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
The first decompression chamber has an unwinding roll for unwinding the long body, a can roll and a sputter cathode around which the long body unwound from the unwinding roll is wound, and one of the long bodies A first sputtering web coater for forming a metal film on the surface, a can roll and a sputter cathode around which the long body having the metal film formed by the first sputtering web coater is wound; A second sputtering web coater for forming a metal film on the other surface is provided; and
In the second decompression chamber, a first plasma reaction chamber for introducing the first reaction gas and a second plasma reaction for introducing the second reaction gas are introduced in the conveying direction of the elongated body carried in through the opening of the partition wall. Forming means for metal oxide film or metal nitride film in which at least one set of chambers are alternately arranged, and a winding roll for winding up the long body on which the metal oxide film or metal nitride film is formed Is provided,
A plurality of roll groups constituting a roll-to-roll conveying means are provided in the first decompression chamber and the second decompression chamber, respectively, in the conveying direction of the long body.

  In the second decompression chamber, the first plasma reaction chamber for introducing the first reaction gas and the second plasma reaction chamber for introducing the second reaction gas are formed by film forming means in which at least one set is alternately arranged. The metal oxide film or metal nitride film is an ultra-thin (several atomic layer or less) film that can be removed by a slight etching process, so it does not adversely affect the wet plating process. (This is a resin film with a metal base layer of Patent Document 2 and requires a step of removing the metal oxide film or the metal nitride film before forming a thick metal film on the metal base layer by a wet plating method. ) Can be easily produced.

Explanatory drawing which shows schematic structure of the double-sided film-forming apparatus based on a prior art. BRIEF DESCRIPTION OF THE DRAWINGS Explanatory drawing which shows schematic structure of the double-sided film-forming apparatus based on this invention. Sectional drawing which shows schematic structure of the resin film with a metal base layer which concerns on a prior art (the elongate body by which the metal film which comprises a metal base layer was formed into a film on both surfaces). Sectional drawing which shows schematic structure of the resin film with a metal base layer which concerns on this invention (The elongate body by which the metal film which comprises a metal base layer was formed into a film on both surfaces). Metal having a metal film of a film thickness formed by wet plating on a metal base layer of a resin film with a metal base layer according to the present invention (a long body in which metal films constituting the metal base layer are formed on both sides) Sectional drawing which shows schematic structure of a resin film with a film | membrane.

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

(1) Resin film with metal base layer When manufacturing a resin film with a metal film to be applied to a flexible wiring board, as described above, a wet plating method with a high film formation rate and a sputtering method with a low film formation rate are used in combination. The method described in Patent Document 2 is widely used.

  Then, a resin film with a metal film in the previous stage of forming a thick metal film by a wet plating method with a high film formation rate (that is, a long resin film and a metal film formed by sputtering on both surfaces thereof) The resin film with a metal film as a precursor composed of a resin film with a metal base layer used in the method described in Patent Document 2.

(1-1) Resin film with metal base layer according to the prior art The resin film with metal base layer according to the prior art (a long body in which the metal films constituting the metal base layer are formed on both sides) is shown in FIG. As shown, it is composed of a long resin film 1, a metal seed layer 2 formed on both surfaces by a sputtering method, and a metal base layer 3 formed on the metal seed layer 2 by a sputtering method. Has been.

  Then, a thick metal film is formed on the metal base layer 3 of the resin film with a metal base layer shown in FIG. 3 by a wet plating method to obtain a resin film with a metal film applied to a flexible wiring board. .

  In addition, immediately after the metal seed layer 2 and the metal base layer 3 are continuously formed on both sides of the long resin film 1 by the sputtering method, the surface activity of the metal film such as the metal base layer 3 is high. Therefore, when the long resin film 1 on which the metal base layer 3 or the like is formed is wound on a take-up roll, a blocking phenomenon occurs in which the metal films stick to each other as described above. There is a problem that the metal film formed on one surface of the film 1 is peeled off and stuck on the other surface, or a film wrinkle is generated.

(1-2) Resin Film with Metal Base Layer According to the Present Invention A resin film with a metal base layer according to the present invention (a long body in which metal films constituting the metal base layer are formed on both sides) is shown in FIG. As shown, a long resin film 11, a metal seed layer 12 formed on both surfaces of the resin film 11 by sputtering, and a metal base layer 13 formed on the metal seed layer 12 by sputtering. The anti-blocking layer 14 made of a metal oxide film or a metal nitride film is formed on the metal base layer 13 by an atomic layer deposition (ALD) method.

  When the thick metal film is formed by the wet plating method, the anti-blocking layer 14 shown in FIG. 4 is removed by etching, and on the metal base layer 13 formed by the sputtering method as shown in FIG. The metal layer 18 is formed by a wet plating method to obtain a resin film with a metal film that is applied to a flexible wiring board.

  The anti-blocking layer 14 made of a metal oxide film or metal nitride film formed by the ALD method is an extremely thin film (several atomic layers or less) that can be removed by a slight etching process. It has the advantage of not adversely affecting the wet plating process.

  Further, the precursor before the metal layer 18 is formed, that is, the long resin film 11, the metal seed layer 12 formed by sputtering on both surfaces of the resin film 11, and the metal seed layer 12 A precursor composed of a metal base layer 13 formed by a sputtering method and an anti-blocking layer 14 made of a metal oxide film or a metal nitride film formed on the metal base layer 13 by an ALD method is provided. As described above, it is a resin film with a metal base layer according to the present invention.

  In addition, as a long resin film (long body) applicable in the present invention, for example, a polyimide film, a polyamide film, a polyester film, a polytetrafluoroethylene film, a polyphenylene sulfide film, a polyethylene naphthalate film Fluorine-based resin films such as liquid crystal polymer film and polytetrafluoroethylene film are preferable, because it has flexibility as a flexible substrate with a metal film, practically necessary strength, and electrical insulation suitable as a wiring material. .

(2) Double-sided film forming method The double-sided film forming method according to the present invention is a method of forming a metal film on both sides of a long resin film (long body) conveyed by a roll-to-roll under a reduced pressure atmosphere. so,
A first film forming step of forming a metal film on one surface of the long body by a first sputtering means having a can roll and a sputter cathode provided on the conveying path of the long body;
A second film forming step of forming a metal film on the other surface of the elongated body by a second sputtering means having a can roll and a sputter cathode provided on a downstream conveyance path of the first sputtering means;
A third composition in which a metal oxide film or a metal nitride film is formed by atomic layer deposition (ALD) on at least one metal film of the elongated body on the downstream transport path of the second sputtering means. A membrane process;
A winding step of winding a long body on which a metal oxide film or a metal nitride film is formed, 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 anti-blocking layer 14 is made of a metal oxide film or metal nitride film that is formed by an ALD method and is very thin (several atomic layers or less) and has no pinholes.

(2-1) ALD method In the atomic layer deposition (ALD) method, as described above, the source gas containing the elements constituting the molecular layer (atomic layer) is alternately introduced into the vacuum apparatus, and vacuum is applied. The film thickness of the layer to be deposited by the method of depositing a single atom (monomolecular) layer by the reaction between the molecules adsorbed on the outermost surface of the deposition target placed in the apparatus and the source gas introduced next. This can be controlled at the atomic layer level.

  And since the ALD method is a method in which film formation starts while depositing a single atom (monomolecular) layer from the deposition target side, the metal film formed on both sides of the long resin film (long body) Thus, it is possible to form an anti-blocking layer made of a metal oxide film or metal nitride film without pinholes.

  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, the ALD method can form a uniform film even on the surface of a film to be deposited, which is difficult to form by a sputtering method or a vacuum evaporation method, which have high straightness.

  And when a long resin film (long body) with a metal film formed on both sides is used for a resin film with a metal base layer, a slight etching process that does not greatly affect the subsequent wet plating process There is no method other than the ALD method that can form an ultra-thin (several atomic layer or less) metal oxide film or metal nitride film (blocking prevention layer) that can be removed in a state without pinholes. 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. Therefore, there is no phenomenon in which the splash adheres to the metal oxide film or metal nitride film being formed and falls off to form a pinhole. In addition, since 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, the film formation cost is reduced as compared with the conventional film formation method. Can also be planned.

  Next, in the ALD method, the first reaction gas (source gas) and the second reaction gas (source gas) containing each of the elements constituting the molecular layer are alternately introduced into the vacuum apparatus (decompression chamber) below. The A to I steps shown in FIG. 1 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 ₃ , ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , and TiO ₂ , nitride films such as AlN, TaN, TiN, TaSiN, and 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 (i) to (iv).

(I) Introducing water molecules as the first reaction gas 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
(Ii) Purge and exhaust excess water molecules.
(Iii) 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
(Iv) 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 subject the film formation body to a treatment such as heating to 100 to 300 ° C.

  Table 1 shows examples of combinations of the first reaction gas and the second reaction gas for forming the metal oxide film or the metal nitride film constituting the anti-blocking layer in the method for producing a resin film with a metal base layer according to the present invention. Show.

（注）
「Ｍｅ」： Methyl
「Ｅｔ」： Ethyl
「ＯＭｅ」： Methoxy
「ＯＥｔ」： Ethoxy
「ａｃａｃ」： Acetylaceto-nato
「ｔｈｄ」： 2, 2, 6, 6-Tetramethyl-3, 5-heptanedionate
「ａｐｏ」： 2-Amino-Pent-2-en-4-onate
「ｄｍｇ」：Dimethyl-glyoximato
「ｈＦａｃ」： 1, 1, 1, 5, 5-HexaFluoro-acetylacetonto

(note)
"Me": Methyl
“Et”: Ethyl
“OMe”: Methoxy
“OEt”: Ethoxy
“Acac”: Acetylaceto-nato
“Thd”: 2, 2, 6, 6-Tetramethyl-3, 5-heptanedionate
“Apo”: 2-Amino-Pent-2-en-4-onate
“Dmg”: Dimethyl-glyoximato
“HFac”: 1, 1, 1, 5, 5-HexaFluoro-acetylacetonto

(3) Double-sided film forming apparatus (sputtering web coater) according to the prior art
As shown in FIG. 1, the double-sided film forming apparatus (sputtering web coater) according to the prior art winds the unwinding roll 20 and the long resin film F for unwinding the long resin film (long body) F. A take-up roll 36 is provided in a vacuum device (decompression chamber), and a metal film (metal) is formed on one surface of the long resin film F on a conveyance path between the take-up roll 20 and the take-up roll 36. A first sputtering web coater for forming a seed layer and a metal base layer), and a second for forming a metal film (metal seed layer and metal base layer) on the other surface of the long resin film F. A sputtering web coater is provided.

  The first sputtering web coater includes a water-cooled temperature-controlled can roll 24 and four magnetron sputter cathodes 40, 41, 42, 43 arranged along the outer peripheral surface. The web coater includes a water-cooled temperature-controlled can roll 32 and four magnetron sputter cathodes 44, 45, 46, 47 arranged along the outer peripheral surface.

  A plurality of free rolls 21, 22, 23, 25, 26, 27, 28, 29, 31, 33 constituting a roll-to-roll conveying means are provided between the unwinding roll 20 and the winding roll 36. , 34, and 35 are provided over the conveying direction of the long resin film F, respectively.

  The unwinding roll 20 and the winding roll 36 are kept in tension balance by a powder clutch or the like, and the long resin film F is conveyed by the rotation of the water-cooled can rolls 24 and 32. The above-described free rolls 21, 22, 23, 25, 26, 27, 28, 29, 31, 33, 34, and 35 having no drive unit are provided between the unwinding roll 20 and the winding roll 36. However, when a control method is adopted in which the long resin film F is brought into close contact with the outer peripheral surfaces of the can rolls 24, 32 by tension, a tension sensor is attached to the free rolls 22, 26, 29, 34. There is also. Moreover, when the method of making the elongate resin film F contact | adhere to the outer peripheral surface of the can rolls 24 and 32 by peripheral speed difference control is taken, the free rolls 23, 25, 31, and 33 may become a drive roll.

  In addition, a surface treatment unit that performs plasma treatment or ion beam treatment in which argon gas, oxygen gas, or the like is introduced at a position before forming a metal film using the first sputtering web coater and the second sputtering web coater (see FIG. It is also possible to arrange them. By disposing the surface treatment unit, both surfaces of the long resin film F can be cleaned and activated.

  The long resin film F unwound from the unwinding roll 20 is a film forming region of a first sputtering web coater and a second sputtering web coater each having a water-cooled temperature-controlled can roll and four magnetron sputtering cathodes. It is conveyed to. In the film formation region of the first sputtering web coater, four magnetron sputter cathodes 40, 41, 42, 43 (for example, magnetron sputter cathodes) on which metal targets for forming the metal seed layer and the metal base layer are attached. One of the long resin films F wound around the outer peripheral surface of the can roll 24 which is temperature-cooled using a metal seed layer 40 and a magnetron sputter cathode 41, 42, 43 for forming a metal base layer). A metal film composed of a metal seed layer and a metal base layer is formed on the surface (referred to as a first film formation surface), and further four metal targets for metal seed layer formation and metal base layer formation are attached. Magnetron sputter cathodes 44, 45, 46, 47 (for example, the magnetron sputter cathode 44 is a metal seed layer) The other surface of the long resin film F wound around the outer peripheral surface of the can roll 32 that has been subjected to water cooling using the composition and magnetron sputter cathodes 45, 46, 47 for forming the metal base layer (second surface) A metal film composed of a metal seed layer and a metal base layer is formed on the film formation surface.

  In addition, it is preferable to use a plate-like target for the sputtering film formation of the metal base layer. However, when the 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.

  By the way, the metal film (metal seed layer and metal base layer) is formed on the first film formation surface and the second film formation surface of the long resin film F by using the double-sided film formation apparatus (sputtering web coater). The long resin film F is wound around the take-up roll 36 and the long resin film (heat-resistant resin film with metal base layer) F after film formation is unwound by wet plating in the next step. In this case, the films stick to each other due to blocking, and the metal base layer or the metal seed and the metal base layer may be peeled off if the film is forcibly peeled off. Web coater) had room for improvement.

(4) Double-sided film forming apparatus according to the present invention A metal film (metal seed layer and metal base layer) is formed on one surface (first film-forming surface) of the long resin film (long body) by the first sputtering means. And forming a metal film (metal seed layer and metal base layer) on the other surface (second film formation surface) of the long resin film by the second sputtering means, and at least the long resin film A double-sided composition according to the present invention in which an anti-blocking layer made of a metal oxide film or a metal nitride film is formed on one metal film (metal seed layer and metal base layer) by an atomic layer deposition (ALD) method. A membrane device (device for producing a resin film with a metal base layer) includes a second decompression chamber provided adjacent to the first decompression chamber via a first decompression chamber and a partition, and the first decompression chamber includes Unwind the long resin film An unwinding roll, a can roll on which a long resin film unwound from the unwinding roll is wound, and a sputter cathode, and metal on one surface (first film-forming surface) of the long resin film A first sputtering web coater for forming a film (metal seed layer and metal base layer), a can roll and a sputter cathode around which a long resin film having the metal film formed thereon is wound by the first sputtering web coater. And a second sputtering web coater for forming a metal film (metal seed layer and metal base layer) on the other surface (second film-forming surface) of the long resin film, In the decompression chamber, a first plasma reaction chamber for introducing a first reaction gas in the transport direction of the long resin film carried in through the opening of the partition wall and the first plasma reaction chamber Deposition means for forming a metal oxide film or metal nitride film (blocking prevention layer) in which at least one or more second plasma reaction chambers for introducing a reaction gas are alternately arranged, and the metal oxide film or metal nitride film A take-up roll that winds up the long resin film on which the (anti-blocking layer) is formed is provided, and a plurality of roll groups constituting a roll-to-roll conveying means are formed of the long resin film. The first and second decompression chambers are provided in the transport direction, respectively.

  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 oxide film or a metal nitride film (anti-blocking layer) by the ALD method on a continuous resin film (long body) that is continuously conveyed, Is arranged with at least one or more pairs of the first reaction chamber for introducing the first reaction gas and the second reaction chamber for introducing the second reaction gas in the second decompression chamber in the conveying direction of the long resin film. It adopts a configuration to do. In the double-sided film forming apparatus according to the present invention, the first decompression in which at least one or more pairs of the first reaction chamber for introducing the first reaction gas and the second reaction chamber for introducing the second reaction gas are alternately arranged. By passing a long resin film (long body) through the chamber region, a metal oxide film or metal nitride film (anti-blocking layer) is formed while each reaction of the ALD method described above is performed in each reaction chamber. Is done.

  In the double-sided film forming apparatus according to the present invention, a second decompression chamber in which a metal oxide film or a metal nitride film (antiblocking layer) is formed by an ALD method, and a metal film (metal seed layer) by a sputtering method Since the gas pressure suitable for film formation differs between the first decompression chamber where the film formation of the metal base layer and the metal base layer) is performed, each decompression chamber is partitioned by the partition wall, and the gas suitable for each film formation by differential exhaust It is necessary to keep the pressure. In the ALD method, it is desirable to perform a treatment such as heating on the film formation target as described above in order to promote the reaction.

(5) Manufacturing apparatus of resin film with metal base layer The manufacturing apparatus of the resin film with metal base layer used in the manufacturing method of the resin film with metal base layer to which the double-sided film forming method according to the present invention is applied is shown in FIG. As shown in the figure, a first decompression chamber 90 and a second decompression chamber 91 provided adjacent to the first decompression chamber 90 via a partition wall 92 are provided. 65 is provided.

  First, in the first decompression chamber 90, an unwinding roll 50 for unwinding a long resin film (long body) F, and one surface (first film formation) of the unrolled long resin film F. A first sputtering web coater for forming a metal film (metal seed layer and metal base layer) on the surface), and a metal film (metal seed layer and metal base layer) on the other surface of the long resin film F. A second sputtering web coater is provided. The first sputtering web coater is composed of a water-cooled temperature-controlled can roll 54 and four magnetron sputter cathodes 70, 71, 72, 73 arranged along the outer peripheral surface. The web coater includes a water-cooled temperature-controlled can roll 61 and four magnetron sputter cathodes 74, 75, 76, 77 arranged along the outer peripheral surface.

  On the other hand, the first reaction chambers 80 and 82 for introducing the first reaction gas into the second decompression chamber 91 through the opening direction 65 of the partition wall 92 in the transport direction of the long resin film F and the second reaction chamber 80 are provided. A metal oxide film or metal nitride film forming means by the ALD method in which two sets of second reaction chambers 81 and 83 for introducing a reaction gas are alternately arranged, and the metal oxide film or metal nitride film ( Winding rolls 66 for winding the long resin film F on which the anti-blocking layer is formed are provided.

  In addition, the first decompression chamber 90 in which a metal film (metal seed layer and metal base layer) is formed by sputtering and the second decompression chamber 91 in which an anti-blocking layer is formed by ALD are formed. Since the gas pressure suitable for each is different, each region is partitioned by the partition 80 having the opening 65 in which the slit roll is incorporated, and differential exhaust is performed.

  A plurality of free rolls 51, 52, 53, constituting a roll-to-roll conveying means are provided between the unwinding roll 50 in the first decompression chamber 90 and the take-up roll 66 in the second decompression chamber 91. 55, 56, 57, 58, 59, 60, 62, 63, 64, 67, 68 are provided over the transport direction of the long resin film F, respectively.

  Then, the long resin film F is unwound from the unwinding roll 50 in the first decompression chamber 90 and taken up by the take-up roll 66 in the second decompression chamber 91. Further, the unwinding roll 50 and the winding roll 66 are kept in tension balance by a powder clutch or the like, and the long resin film F is conveyed by the rotation of the water-cooled temperature-controlled can rolls 54 and 61. Further, the above-described free rolls 51, 52, 53, 55, 56, 57, 58, 59, 60, 62, 63, 64, 67 having no drive unit are not provided between the unwinding roll 50 and the winding roll 66. 68, but when a control method is adopted in which the long resin film F is brought into close contact with the outer peripheral surfaces of the can rolls 54, 61 by tension, a tension sensor is provided on the free rolls 52, 56, 59, 63. Sometimes attached. Moreover, when the method of making the elongate resin film F contact | adhere to the outer peripheral surface of the can rolls 54 and 61 by peripheral speed difference control is taken, the free rolls 53, 55, 60, and 62 may become a drive roll.

  In addition, a surface treatment unit that performs plasma treatment or ion beam treatment in which argon gas, oxygen gas, or the like is introduced at a position before forming a metal film using the first sputtering web coater and the second sputtering web coater (see FIG. It is also possible to arrange them. By disposing the surface treatment unit, both surfaces of the long resin film F can be cleaned and activated.

  The long resin film F unwound from the unwinding roll 50 in the first decompression chamber 90 includes a first sputtering web coater and a second sputtering each having a water-cooled temperature-controlled can roll and four magnetron sputtering cathodes, respectively. It is transferred to the film forming area of the web coater. In the film formation region of the first sputtering web coater, four magnetron sputter cathodes 70, 71, 72, 73 (for example, magnetron sputter cathodes) on which metal targets for forming the metal seed layer and the metal base layer are attached. One of the long resin films F wound around the outer peripheral surface of the can roll 54 which is temperature-cooled by using a metal seed layer formation 70 and a magnetron sputter cathode 71, 72, 73 for metal base layer formation) 4 magnetrons on which a metal film comprising a metal seed layer and a metal base layer is formed on the surface (first film formation surface), and a metal target for forming the metal seed layer and a metal base layer are attached. Sputter cathode 74, 75, 76, 77 (for example, magnetron sputter cathode 74 is used for forming a metal seed layer, The other surface (second film formation) of the long resin film F wound on the outer peripheral surface of the can roll 61 whose temperature is cooled by water using the magnetron sputter cathodes 75, 76, and 77 are used for forming a metal base layer. After a metal film composed of a metal seed layer and a metal base layer is formed on the surface), the metal film is carried from the first decompression chamber 90 into the second decompression chamber 91 through the opening 65 of the partition wall 92.

  The long resin film F on which a metal film composed of a metal seed layer and a metal base layer is formed has a first reaction chamber 80 and a second reaction gas into which the first reaction gas in the second decompression chamber 91 is introduced. Is passed through the second reaction chamber 81 into which the first reaction gas has been introduced, the second reaction chamber 82 into which the second reaction gas has been introduced, so that the reaction by the ALD method described above can be performed. As a result, a two-atom (molecule) layer anti-blocking layer (metal oxide film or metal nitride film) is formed on both sides. In order to increase the atomic layer of the blocking prevention layer, 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 may be added. A long resin film F in which an antiblocking layer is formed on each metal film composed of a metal seed layer and a metal base layer is wound around a take-up roll 66 in the second decompression chamber 91, and according to the present invention. A resin film with a metal base layer is obtained.

  The resin film with a metal base layer manufactured by the apparatus for manufacturing a resin film with a metal base layer has a blocking phenomenon because the metal film does not come into contact with each other when the anti-blocking layer is interposed when the resin film with the metal base layer is wound around the winding roll 66. And the metal base layer does not stick to and peel off from the metal base layer on the contact side.

  In addition, when forming a metal layer having a film thickness on the metal base layer of the obtained resin film with a metal base layer using a wet plating method, the electroplating process is performed as the primary plating or only when the electroplating process is performed. In some cases, the secondary plating may be performed in combination with a wet plating method such as electrolytic plating. The wet plating process may employ various conditions of a conventional wet plating method.

  The antiblocking layer (metal oxide film or metal nitride film) is an extremely thin film (several atomic layers or less) and can be easily removed by an etching process before wet plating.

  In addition, it is preferable that the total thickness of the metal film (metal base layer and metal layer) by dry (sputtering method) / wet plating method is 18 μm or less.

(6) Use of resin film with metal film Using the resin film with a metal film thus obtained, a wiring pattern is individually formed on at least one surface of the resin film with a metal film. In addition, via holes for interlayer connection can be formed at predetermined positions and used for various purposes. Specifically,
(A) A high-density wiring pattern is individually formed and used on at least one surface of a flexible sheet.
(B) A via hole penetrating the wiring layer and the flexible sheet is formed on the flexible sheet on which the wiring layer is formed.
(C) In some cases, the via hole is filled with a conductive substance to make the hole conductive and used.

  As a method for forming the wiring pattern, a conventionally known method such as photoetching can be used. For example, a resin film with a metal film is prepared, and screen printing or a 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.

[Example 1]
Using a double-sided film forming apparatus (manufacturing apparatus for a metal base layer-attached resin film) shown in FIG. 2, a long resin film (long body) F has a width of 500 mm, a length of 1000 m, and a thickness of 25 μm. A company-made heat-resistant polyimide film “Kapton (registered trademark)” was used.

The anti-blocking layer formed by the ALD method is made of Al ₂ O ₃ for both atomic layers, and water molecules of the first reaction gas are introduced into the first reaction chambers 80 and 81 at 10 sccm / min for the second reaction. The chambers 82 and 83 were introduced with 50 mg / min of TMA [Trimethyl Aluminum: Al (CH ₃ ) ₃ ] gas as the second reaction gas. Each of the reaction chambers 80, 81, 82, 83 is independently set toward the back of the second decompression chamber 91 while the temperature is set to 200 ° C. and the reaction gas is continuously introduced from the front of the second decompression chamber 91. The air was exhausted with a dry pump.

  The metal seed layer of the metal film (metal seed layer and metal base layer) is a Ni—Cr alloy film, and each magnetron sputtering cathode 70, 74 uses a magnetron sputtering target made of a Ni—Cr alloy, and the above metal The base layer is a Cu film, a magnetron sputtering target made of Cu is used for each of the magnetron sputtering cathodes 71, 72, 73, 75, 76, 77, and argon gas is introduced into each magnetron sputtering cathode at 300 sccm. Film formation was performed at 10 kW. The tension between the unwinding roll 50 and the winding roll 66 was 80N.

  And the heat-resistant polyimide film (long body) F is set to the unwinding roll 50 of the 1st decompression chamber 90, and it makes it pass through the can roll 54 and the can roll 61, and also each reaction of the 2nd decompression chamber 91 The tip of the heat-resistant polyimide film (long body) F was attached to the take-up roll 66 of the second decompression chamber 91 through the chambers 80 to 83. In addition, the heat-resistant polyimide film (long body) F to be used is vacuum-dried beforehand.

Further, after each of the first decompression chamber 90 for film formation by sputtering and the second decompression chamber 91 for film formation by ALD is evacuated to 5 Pa by a large dry pump, film formation by sputtering is further performed. The first decompression chamber 90 was evacuated to 5 × 10 ⁻³ Pa using a turbo molecular pump and a cryocoil. Moreover, the set value of the water cooling temperature control in each of the can rolls 54 and 61 was 20 ° C.

  And after making the conveyance speed of the said heat-resistant polyimide film (long body) F into 2 m / min, argon gas is introduce | transduced into each magnetron sputter cathode 70-77 of the 1st decompression chamber 90, and electric power is supplied to each magnetron sputter cathode. Was applied to the reaction chambers 80, 81, 82, 83 of the second decompression chamber 91 to start the film formation process.

  At the time when the length of 990 m of the heat-resistant polyimide film F passed, the power to each magnetron sputter cathode was stopped, and the introduction of each gas was also stopped.

  Finally, the conveyance of the heat-resistant polyimide film F is stopped, and after stopping each pump, the first decompression chamber 90 and the second decompression chamber 91 are vented (open to the atmosphere), and the heat-resistant polyimide of the unwinding roll 50 The terminal portion of the film F was removed, and all the heat-resistant polyimide film F was taken up on the take-up roll 66 and then removed.

  And when the manufactured resin film with a metal base layer is set to “film rewinding” and rewinding at a conveyance speed of 10 m / min, no blocking phenomenon is observed, and further, the sampled sheet is observed with a microscope. However, there was no place where the metal films (metal seed layer and metal base layer) adhered to each other and were partly peeled off.

  Further, a part of the manufactured resin film with a metal base layer is cut out, and a first film formation surface (a metal seed layer and a metal base layer formed on one surface of the heat-resistant polyimide film F), and a second composition The film surface (metal seed layer and metal base layer formed on the other surface of the heat-resistant polyimide film F) is partially etched to form a metal film (metal) formed on the first film formation surface and the second film formation surface. As a result of measuring the film thickness of the seed layer and the metal base layer with a fluorescent X-ray film thickness meter, the metal seed layer was about 30 nm and the metal base layer was about 100 nm on both the first film formation surface and the second film formation surface. It was.

Thereafter, the surface of the metal base layer of the produced resin film with a metal base layer is washed with an acid, the anti-blocking layer (Al ₂ O ₃ ) is removed by the ALD method, and then the entire Cu is formed by electrolytic plating with an aqueous copper sulfate solution. A metal layer was formed until the film thickness became 8 μm, and a resin film with a metal film according to Example 1 was obtained.

  When the obtained resin film with a metal film was sampled and surface irregularities were observed with a microscope, irregularities due to blocking were not found.

Although forming the anti-blocking layer according to Example 1, _{Al 2 O 3, Al 2 O} 3 other than the metal oxide film (Ti, Zn, Ce, metal oxide selected Ni, Sn, Si, from Cu Material film) or a metal nitride film (a metal nitride film selected from Ti, Zn, Ce, Ni, Sn, Si, Al, and Cu) may be employed.

[Comparative Example 1]
The double-sided film forming apparatus according to the prior art shown in FIG. 1 is used, and the long resin film (long body) F has a width of 500 mm, a length of 1000 m, and a thickness of 25 μm, as in Example 1. A company-made heat-resistant polyimide film “Kapton (registered trademark)” was used.

  Similarly to Example 1, the metal seed layer of the metal film (metal seed layer and metal base layer) is a Ni—Cr alloy film, and each magnetron sputtering cathode 40, 44 is provided with a magnetron sputtering target made of a Ni—Cr alloy. In addition, the metal base layer is a Cu film, a magnetron sputtering target made of Cu is used for each of the magnetron sputtering cathodes 41, 42, 43, 45, 46, and 47, and argon gas is supplied to each magnetron sputtering cathode at 300 sccm. Then, film formation was performed at a cathode power of 10 kW. The tension between the unwinding roll 20 and the winding roll 36 was 80N.

  And the heat resistant polyimide film F was set to the unwinding roll 20, and the front-end | tip part of the said heat resistant polyimide film F was attached to the winding roll 36 through the can roll 24 and the can roll 32. FIG. In addition, the heat-resistant polyimide film F to be used has been vacuum-dried in advance.

Further, the can roll 24 and the can roller 32 is installed a vacuum chamber (decompression chamber to form a film by sputtering) was evacuated to 5Pa by large dry pump, further, with a turbo-molecular pump and a cryogenic coil 5 × 10 ^{- The} air was exhausted to ³ Pa. Moreover, the set value of the water cooling temperature control in each of the can rolls 24 and 32 was 20 ° C.

  Then, after the conveyance speed of the heat-resistant polyimide film F is set to 2 m / min, argon gas is introduced into each of the magnetron sputtering cathodes 40 to 47, and electric power is applied to each of the magnetron sputtering cathodes to start a film forming process by sputtering. did.

  At the time when the length of 990 m of the heat-resistant polyimide film F passed, the power to each magnetron sputter cathode was stopped, and the introduction of each gas was also stopped.

  Finally, the conveyance of the heat-resistant polyimide film F is stopped, and after stopping each pump, the decompression chamber in which the can roll 24 and the can roll 32 are installed is vented (open to the atmosphere), and the heat resistance of the unwinding roll 20 is reached. The end of the conductive polyimide film F was removed, and all the heat-resistant polyimide film F was taken up on the take-up roll 36 and then removed.

  Then, when the manufactured resin film with a metal base layer is set to “film rewinding” and rewinding is performed at a conveyance speed of 10 m / min, the attached metal film is peeled off with a crackling sound. Further, when the sampled sheet was observed with a microscope, there were innumerable places where the metal films (metal seed layer and metal base layer) were adhered to each other and partly separated.

  Further, a part of the manufactured resin film with a metal base layer is cut out, and a first film formation surface (a metal seed layer and a metal base layer formed on one surface of the heat-resistant polyimide film F), and a second composition The film surface (metal seed layer and metal base layer formed on the other surface of the heat-resistant polyimide film F) is partially etched to form a metal film (metal) formed on the first film formation surface and the second film formation surface. As a result of measuring the film thickness of the seed layer and the metal base layer with a fluorescent X-ray film thickness meter, the metal seed layer was about 30 nm and the metal base layer was about 100 nm on both the first film formation surface and the second film formation surface. It was.

  Thereafter, a metal layer is formed on the metal base layer of the manufactured resin film with a metal base layer by an electrolytic plating method using an aqueous copper sulfate solution until the total film thickness of Cu becomes 8 μm. A coated resin film was obtained.

  When the obtained resin film with a metal film was sampled and observed for surface irregularities with a microscope, many irregularities due to blocking were found.

  According to the double-sided film forming method and apparatus therefor according to the present invention, a resin film with a metal base layer having no blocking phenomenon can be easily produced. Therefore, a resin film with a metal film obtained from the resin film with a metal base layer is used as a liquid crystal television. The present invention has industrial applicability applicable to flexible wiring boards such as mobile phones.

DESCRIPTION OF SYMBOLS 1,11 Resin film 2,12 Metal seed layer 3,13 Metal base layer 14 Blocking prevention layer (metal oxide film or metal nitride film)
18 Metal layer F Long resin film (long body)
20 Unwinding roll 24, 32 Cooling can roll 21, 22, 23, 25, 26, 27 Free roll 28, 29, 31, 33, 34, 35 Free roll 36 Winding roll 40, 41, 42, 43 Magnetron sputter cathode 44, 45, 46, 47 Magnetron sputtering cathode 50 Unwinding roll 54, 61 Cooling can roll 51, 52, 53, 55, 56, 57, 58 Free roll 59, 60, 62, 63, 64, 67, 68 Free roll 66 Winding rolls 70, 71, 72, 73 Magnetron sputter cathodes 74, 75, 76, 77 Magnetron sputter cathodes 80, 82 First reaction chamber 81, 83 Second reaction chamber 90 First decompression chamber 91 Second decompression chamber 92 Bulkhead 65 opening

Claims (5)

In a double-sided film forming method for forming a metal film on both sides of a long body conveyed by a roll-to-roll under a reduced pressure atmosphere,
A first film forming step of forming a metal film on one surface of the long body by a first sputtering means having a can roll and a sputter cathode provided on the conveying path of the long body;
A second film forming step of forming a metal film on the other surface of the elongated body by a second sputtering means having a can roll and a sputter cathode provided on a downstream conveyance path of the first sputtering means;
A third composition in which a metal oxide film or a metal nitride film is formed by atomic layer deposition (ALD) on at least one metal film of the elongated body on the downstream transport path of the second sputtering means. A membrane process;
A winding step of winding a long body on which a metal oxide film or a metal nitride film is formed, on a winding roll;
And the first film forming process, the second film forming process, and the third film forming process are successively performed.   The metal oxide film or metal nitride film formed in the third film forming step is at least one metal oxide film or metal nitride selected from Ti, Zn, Ce, Ni, Sn, Si, Al, and Cu. The double-sided film forming method according to claim 1, wherein the double-sided film forming method is a physical film.   The double-sided film forming method according to claim 1 or 2, wherein the elongated body is composed of one selected from a polyimide film, an aramid film, a liquid crystal polymer, and a polytetrafluoroethylene film. A metal film is formed on one surface of the long body by the first sputtering means, a metal film is formed on the other surface of the long body by the second sputtering means, and at least one of the above metals of the long body In a double-sided film forming apparatus for forming a metal oxide film or a metal nitride film on the film by an atomic layer deposition (ALD) method,
A first decompression chamber and a second decompression chamber provided adjacent to the first decompression chamber via a partition;
The first decompression chamber has an unwinding roll for unwinding the long body, a can roll and a sputter cathode around which the long body unwound from the unwinding roll is wound, and one of the long bodies A first sputtering web coater for forming a metal film on the surface, a can roll and a sputter cathode around which the long body having the metal film formed by the first sputtering web coater is wound; A second sputtering web coater for forming a metal film on the other surface is provided; and
In the second decompression chamber, a first plasma reaction chamber for introducing the first reaction gas and a second plasma reaction for introducing the second reaction gas are introduced in the conveying direction of the elongated body carried in through the opening of the partition wall. Forming means for metal oxide film or metal nitride film in which at least one set of chambers are alternately arranged, and a winding roll for winding up the long body on which the metal oxide film or metal nitride film is formed Is provided,
A double-sided film forming apparatus characterized in that a plurality of roll groups constituting a roll-to-roll conveying means are respectively provided in the first decompression chamber and the second decompression chamber in the conveying direction of the long body. The long body is composed of a long resin film, and the metal film formed on both sides of the long body is composed of a metal seed layer and a metal base layer formed on the metal seed layer. In the manufacturing method of the resin film with a metal base layer,
The double-sided film forming method according to any one of claims 1 to 3, wherein the metal seed layer is made of a Ni alloy, the metal base layer is made of Cu or a Cu alloy, and the metal seed layer and the metal base layer are formed. A method for producing a resin film with a metal base layer, characterized in that the film is formed by:

Images