WO2016084605A1 - 積層体フィルムと電極基板フィルムおよびこれ等の製造方法 - Google Patents

積層体フィルムと電極基板フィルムおよびこれ等の製造方法 Download PDF

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WO2016084605A1
WO2016084605A1 PCT/JP2015/081762 JP2015081762W WO2016084605A1 WO 2016084605 A1 WO2016084605 A1 WO 2016084605A1 JP 2015081762 W JP2015081762 W JP 2015081762W WO 2016084605 A1 WO2016084605 A1 WO 2016084605A1
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Prior art keywords
film
metal
transparent substrate
absorption layer
layer
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PCT/JP2015/081762
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English (en)
French (fr)
Japanese (ja)
Inventor
寛人 渡邉
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住友金属鉱山株式会社
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Priority to JP2016533736A priority Critical patent/JP6249101B2/ja
Publication of WO2016084605A1 publication Critical patent/WO2016084605A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to a laminate film having a transparent substrate made of a resin film and a laminate film, and an electrode substrate film produced by etching the laminate film of the laminate film and used for a touch panel or the like.
  • the present invention relates to a laminate film, an electrode substrate film, and a method of manufacturing the same, which are excellent in the above-mentioned and in which a circuit pattern formed by etching treatment is hardly visible even under high-luminance illumination.
  • the “touch panel” is roughly divided into a resistance type and a capacitance type.
  • a “resistive touch panel” is a transparent substrate made of a resin film, an X coordinate (or Y coordinate) detection electrode sheet provided on the substrate, and a Y coordinate (or X coordinate) detection electrode sheet, and a space between these sheets The main part is comprised with the insulator spacer provided in this.
  • the X-coordinate detection electrode sheet and the Y-coordinate detection electrode sheet are spatially separated from each other.
  • the “capacitance-type touch panel” has an X-coordinate (or Y-coordinate) detection electrode sheet and a Y-coordinate (or X-coordinate) detection electrode sheet laminated via an insulating sheet. It has a structure in which an insulator is disposed. When a finger is brought close to the insulator such as glass, the electric capacity of the X-coordinate detection electrode and the Y-coordinate detection electrode in the vicinity thereof changes so that the position can be detected.
  • a transparent conductive film such as ITO (indium oxide-tin oxide) has been widely used (see Patent Document 1). Further, along with the increase in the size of touch panels, metal fine wires (metal films) having a mesh structure disclosed in Patent Document 2, Patent Document 3, and the like have begun to be used.
  • the transparent conductive film When the transparent conductive film is compared with a thin metal wire (metal film), the transparent conductive film has an advantage that the circuit pattern such as an electrode is hardly visually recognized because of its excellent transparency in the visible wavelength region. Since the electric resistance value is higher than that of the film), there is a disadvantage that is not suitable for increasing the size of the touch panel and increasing the response speed.
  • thin metal wires metal films are suitable for increasing the size of touch panels and increasing the response speed due to their low electrical resistance, but they have high reflectivity in the visible wavelength region, so they are processed into a fine mesh structure. Even if it is done, a circuit pattern may be visually recognized under high-intensity illumination, and it has the fault of reducing a product value.
  • the said metal absorption layer which consists of metal oxides is a long resin film by reactive sputtering etc. which usually used the metal target (metal material) and reactive gas from the viewpoint of aiming at the film-forming efficiency of a metal oxide.
  • the metal layer is continuously formed on the surface, and the metal layer is continuously formed on the formed metal absorption layer by sputtering using a metal target (metal material) such as copper, and used for the production of the electrode substrate film. Laminate films have been manufactured.
  • the electrode substrate film used for a touch panel or the like is a cupric chloride film made of a laminate film having a transparent substrate made of a resin film and a laminated film made of a metal absorption layer and a metal layer provided on the substrate. It is manufactured by etching with an etching solution such as an aqueous solution or an aqueous ferric chloride solution, and processing the laminated film (metal absorption layer and metal layer) of the laminated film into a circuit pattern such as an electrode.
  • an etching solution such as an aqueous solution or an aqueous ferric chloride solution
  • the laminate film used for the production of the electrode substrate film has characteristics that the laminated film (metal absorption layer and metal layer) is easily etched by an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution, and etching.
  • the circuit pattern such as the processed electrode is required to have a characteristic that it is difficult to be visually recognized under high luminance illumination.
  • JP 2003-151358 A (refer to claim 2) JP 2011-018194 A (refer to claim 1) JP 2013-0669261 A (see paragraph 0004) JP 2014-142462 A (see claim 5, paragraph 0038) JP 2013-225276 A (refer to claim 1, paragraph 0041)
  • a metal absorption layer made of a metal oxide is continuously formed on the long resin film surface by reactive sputtering using a metal target (metal material) such as a Ni-based alloy and a reactive gas containing oxygen.
  • a metal target metal material
  • a metal target metal material such as copper
  • a film formation start side laminate film in which the metal absorption layer is formed in the initial stage of film formation Deposition end side laminate film in which the metal absorbing layer is formed at the end of film formation (deposition end side region of the long laminate film) compared to the film formation start end region of the long laminate film) ) Is inferior in etching property, and due to this, there is a problem that the processing accuracy of the circuit pattern in the electrode substrate film is not stable.
  • the present invention has been made paying attention to such problems, and the problem is that the circuit pattern of etched electrodes and the like is not easily visible even under high-intensity illumination. It is providing a body film and an electrode substrate film, and providing each manufacturing method of a laminated body film and an electrode substrate film together.
  • the present inventor investigated the cause of the poor etching property of the film formation end side laminate film as compared with the film formation start end side laminate film, and examined the improvement measures.
  • the metal absorption layer and the metal layer constituting the laminate film of the laminate film were examined, reactive sputtering using a metal target (metal material) such as a Ni-based alloy and a reactive gas containing oxygen, etc.
  • the metal absorption layer formed by the etching solution such as cupric chloride aqueous solution or ferric chloride aqueous solution compared to the metal layer formed by sputtering using a metal target (metal material) such as copper It was confirmed that etching was difficult. From this, among the metal absorption layer and the metal layer constituting the laminate film of the laminate film, the metal absorption layer made of a metal oxide is related to the quality of etching in the film formation termination side laminate film. Was predicted.
  • Non-Patent Document 1 a Ni film is formed by sputtering using a Ni-based metal target (metal material), and further by reactive sputtering using a Ni-based metal target (metal material).
  • a NiOOH film and a NiO film were formed, and the etching properties with an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution were examined.
  • the films having a fast etching progress were Ni film, NiOOH film, NiO film. The membrane order was confirmed.
  • a NiOOH film in which a part of the deposited metal oxide is easily etched in the laminated film on the film start side (a Ni film having better etching property than the NiOOH film is not a metal oxide but a metal absorbing layer). It is considered that most of the deposited metal oxide is a NiO film (which is harder to be etched than a NiOOH film) in the laminated film on the film formation end side.
  • a change with time of the film formation environment change with time of residual moisture in the vacuum chamber
  • the metal oxide metal absorption layer
  • the time-dependent change in moisture content in the vacuum chamber was measured using a quadrupole mass spectrometer. As shown in FIG. 7, a metal oxide (metal absorption layer) film was formed. Compared to the initial stage, it was confirmed that the amount of water in the vacuum chamber was significantly reduced in the later stage of film formation.
  • the etching property of the film formation end side laminate film is inferior to the film formation start side laminate film as the moisture content in the vacuum chamber decreases.
  • the present invention has been completed through such investigation and technical analysis, and metal oxides (reactive sputtering using a metal target (metal material) such as a Ni alloy and a reactive gas containing oxygen)
  • the reactive gas contains water, the content of hydrogen molecules measured by a quadrupole mass spectrometer provided in the film formation chamber, and an argon atom which is a sputtering gas
  • the hydrogen ion current value and the argon ion current value, respectively, and the ratio of the hydrogen molecule content and the argon atom content detected as the ion current value (H 2 / Ar) is constant.
  • the amount of water contained in the reactive gas is set so that the metal oxide (metal absorption layer) is deposited while compensating for the decrease in residual moisture in the deposition chamber. It is obtained by improving the etching properties of the film.
  • the first invention according to the present invention is: In a laminate film composed of a transparent substrate made of a resin film and a laminate film provided on at least one surface of the transparent substrate,
  • the laminated film has a first metal absorption layer and a second metal layer counted from the transparent substrate side, and the metal absorption layer is made of Ni alone, or Ni, Ti, Al, V, Formed by a reactive film-forming method using a metal material composed of an alloy containing two or more elements selected from W, Ta, Si, Cr, Ag, Mo, and Cu and a reactive gas containing oxygen, and , Characterized in that the reactive gas contains water
  • the second invention is In the laminate film according to the first invention,
  • the metal layer has a thickness of 50 nm to 5000 nm
  • the third invention is In the laminate film according to the first invention,
  • the laminated film has a third metal absorption layer as a third layer counted from the transparent substrate side, and the second metal absorption layer is made of Ni alone, or Ni, Ti, Al
  • the fifth invention is: In an electrode substrate film having a transparent substrate made of a resin film, and a mesh-structured circuit pattern made of metal laminated thin wires provided on at least one surface of the transparent substrate,
  • the metal laminated thin wire has a line width of 20 ⁇ m or less and has a first metal absorption layer and a second metal layer counted from the transparent substrate side, and the metal absorption layer is composed of Ni alone, or , Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and a reaction material using a reactive gas containing oxygen and a metal material made of an alloy containing two or more elements selected from Cu It is formed by a membrane method, and the reactive gas contains water,
  • the sixth invention is: In the electrode substrate film according to the fifth invention, The metal layer has a thickness of 50 nm to 5000 nm,
  • the seventh invention In the electrode substrate film according to the fifth invention,
  • the metal thin multilayer wire has a third metal absorption layer as a third layer as counted
  • a ninth invention includes In the method for producing a laminate film composed of a transparent substrate made of a resin film and a laminate film provided on at least one surface of the transparent substrate,
  • the first metal absorption layer counted from the transparent substrate side of the laminated film was selected from Ni alone, or Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu.
  • the tenth invention is In the method for producing a laminate film according to the ninth invention, The third metal absorption layer of the third layer counted from the transparent substrate side of the laminated film is selected from Ni alone, or Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu.
  • the eleventh invention is In the method for producing a laminate film according to the ninth invention or the tenth invention, The alloy is composed of a Ni-based alloy to which one or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added,
  • the twelfth invention is In the method for producing a laminate film according to the ninth invention or the tenth invention, The content of water contained in the reactive gas is set to an amount that compensates for the decrease in the amount of residual water in the film formation chambers of the first step and the third step,
  • the thirteenth invention is In the method for producing a laminate film according to the twelfth invention, Included in the reactive gas so that the ratio (H 2 / Ar) of the content of hydrogen molecules measured by the gas component detection means provided in the film formation chamber
  • the water content is set to compensate for the decrease in the residual water content in the film forming chambers of the first and third steps
  • the fourteenth invention is In the method for producing a laminate film according to the thirteenth invention,
  • the gas component detection means is composed of a quadrupole mass spectrometer, the hydrogen molecule content measured by the quadrupole mass spectrometer is detected as a hydrogen ion current value, and measured by a quadrupole mass spectrometer.
  • the content of argon atoms is detected as an argon ion current value.
  • the fifteenth aspect of the invention relates to In a method for producing an electrode substrate film having a transparent substrate made of a resin film, and a circuit pattern having a mesh structure made of metal laminated thin wires provided on at least one surface of the transparent substrate,
  • the laminated film of the laminated film according to any one of the first to third inventions is subjected to chemical etching treatment, and wiring processing is performed on the above-mentioned metal laminated thin wire having a line width of 20 ⁇ m or less
  • the sixteenth invention is In a method for producing an electrode substrate film having a transparent substrate made of a resin film, and a circuit pattern having a mesh structure made of metal laminated thin wires provided on at least one surface of the transparent substrate,
  • the laminated film of the laminate film described in the fourth invention is subjected to chemical etching treatment, and the above-mentioned metal laminated thin wire having a line width of 20 ⁇ m or less is subjected to wiring processing.
  • a laminate film according to the present invention comprising a transparent substrate made of a resin film and a laminate film provided on at least one surface of the transparent substrate,
  • the laminated film has a first metal absorption layer and a second metal layer counted from the transparent substrate side, and the metal absorption layer is made of Ni alone, or Ni, Ti, Al, V, Formed by a reactive film-forming method using a metal material composed of an alloy containing two or more elements selected from W, Ta, Si, Cr, Ag, Mo, and Cu and a reactive gas containing oxygen, and The reactive gas contains water.
  • the metal oxide (metal absorption layer) of the laminate film is formed while water is included in the reactive gas to compensate for the reduced amount of moisture in the vacuum chamber. Therefore, it is possible to avoid the problem that the etching property of the film formation end side laminate film is inferior to that of the film formation start side laminate film.
  • the schematic cross-section explanatory drawing of the laminated body film which has a 1st metal absorption layer and a 2nd metal layer on both surfaces of the transparent substrate which consists of a resin film from the transparent substrate side.
  • the first metal absorption layer and the second metal layer are counted on both sides of the transparent substrate made of a resin film from the transparent substrate side, and the metal layer is formed by a dry film formation method and a wet film formation method.
  • the first metal absorption layer, the second metal layer and the third metal absorption layer counted from the transparent substrate side on both sides of the transparent substrate made of a resin film, and the metal layer is dry-type Schematic cross-sectional explanatory drawing of the laminated body film which concerns on this invention formed with the film-forming method and the wet film-forming method.
  • BRIEF DESCRIPTION OF THE DRAWINGS Schematic cross-sectional explanatory drawing of the electrode substrate film which concerns on this invention in which the metal lamination
  • the first laminate film according to the present invention is: Consists of a transparent substrate made of a resin film and a laminated film provided on at least one surface of the transparent substrate,
  • the laminated film has a first metal absorption layer and a second metal layer counted from the transparent substrate side, and the metal absorption layer is made of Ni alone, or Ni, Ti, Al, V, Formed by a reactive film-forming method using a metal material composed of an alloy containing two or more elements selected from W, Ta, Si, Cr, Ag, Mo, and Cu and a reactive gas containing oxygen, and , Characterized in that the reactive gas contains water
  • the second laminate film according to the present invention is Assuming the first laminate film,
  • the laminated film has a third metal absorption layer as a third layer counted from the transparent substrate side, and the second metal absorption layer is made of Ni alone, or Ni, Ti, Al, V, W, Ta, It is formed by a reactive film-forming method using a metal material made of an alloy containing two or more elements
  • the first laminate film includes a transparent substrate 40 made of a resin film as shown in FIG. 1, and a dry film forming method (dry plating method) on both surfaces of the transparent substrate 40. It is comprised by the metal absorption layers 41 and 43 and metal layer 42 and 44 which were formed by.
  • the metal layer may be formed by a combination of a dry film formation method (dry plating method) and a wet film formation method (wet plating method).
  • the metal layers 52 and 54 are formed on the metal absorption layers 51 and 53 by a dry film formation method (dry plating method), and the metal layers 52 and 54 are formed by a wet film formation method (wet plating method).
  • the metal layers 55 and 56 may be used.
  • the metal layers 62 and 64 are formed on the metal absorption layers 61 and 63 by a dry film formation method (dry plating method), and the metal layers 62 and 64 are formed by a wet film formation method (wet plating method).
  • the metal absorbing layer 61 and the second metal absorbing layer 67 are formed on both surfaces of the metal layers denoted by reference numerals 62 and 65, and the metals denoted by reference numerals 64 and 66 are formed.
  • the metal absorption layer 63 and the second metal absorption layer 68 are formed on both sides of the layer because the mesh made of the metal laminated thin wires when the electrode substrate film produced using the laminate film is incorporated in the touch panel. This is to prevent the circuit pattern of the structure from being reflected.
  • the metal absorption layer is made of Ni alone or a metal material made of an alloy containing two or more elements selected from Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and oxygen. It forms by the reactive film-forming method using the reactive gas containing.
  • the Ni-type alloy to which 1 or more types of elements chosen from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu were added is utilized widely, and said Ni As the alloy, a Ni—Cu alloy is preferable.
  • the metal absorption layer becomes transparent when the oxidation of the metal oxide constituting the metal absorption layer proceeds excessively, it is necessary to set the oxidation level to such a level that it becomes a blackened film.
  • the reactive film formation method include magnetron sputtering, ion beam sputtering, vacuum deposition, ion plating, and CVD.
  • the optical constant (refractive index, extinction coefficient) at each wavelength of the metal absorption layer is greatly influenced by the degree of reaction, that is, the degree of oxidation, and is not determined only by a metal material made of a Ni-based alloy.
  • the constituent material (metal material) of the metal layer is not particularly limited as long as it is a metal having a low electric resistance value.
  • a metal having a low electric resistance value For example, Cu alone, or Ti, Al, V, W, Ta, Si, Cr, Ag Cu-based alloy to which one or more selected elements are added, Ag alone, or Ag to which one or more elements selected from Ti, Al, V, W, Ta, Si, Cr, and Cu are added
  • Cu alone is desirable from the viewpoint of circuit pattern workability and resistance.
  • the film thickness of the metal layer depends on the electrical characteristics and is not determined by optical elements, but is usually set to a film thickness at which transmitted light cannot be measured.
  • the desirable thickness of the metal layer is preferably 50 nm or more, more preferably 60 nm or more from the viewpoint of electrical resistance. On the other hand, from the viewpoint of workability for processing the metal layer into a wiring pattern, it is preferably 5 ⁇ m (5000 nm) or less, more preferably 3 ⁇ m (3000 nm) or less.
  • Resin film constituting transparent substrate The material of the resin film applied to the laminate film is not particularly limited. Specific examples thereof include polyethylene terephthalate (PET), polyethersulfone (PES). ), Polyarylate (PAR), polycarbonate (PC), polyolefin (PO), triacetylcellulose (TAC) and norbornene resin material alone, or resin film alone selected from the above resin materials And an acrylic organic film covering one side or both sides of the single body.
  • norbornene resin materials representative examples include ZEONOR (trade name) manufactured by ZEON Corporation, Arton (trade name) manufactured by JSR Corporation, and the like.
  • the electrode substrate film produced using the laminate film according to the present invention is used for a “touch panel” or the like, it is desirable that the resin film has excellent transparency in the visible wavelength region.
  • this film-forming apparatus is called a sputtering web coater, and is used when a film-forming process is continuously and efficiently performed on the surface of a long resin film conveyed by a roll-to-roll method.
  • a film forming apparatus for a long resin film conveyed by a roll-to-roll method is provided in a vacuum chamber 10 as shown in FIG.
  • a predetermined film forming process is performed on the unrolled long resin film 12, and then the film is wound by a winding roll 24.
  • a can roll 16 that is rotationally driven by a motor is disposed in the middle of the conveyance path from the unwind roll 12 to the take-up roll 24. Inside the can roll 16, a coolant whose temperature is adjusted outside the vacuum chamber 10 circulates.
  • the pressure is reduced to an ultimate pressure of about 10 ⁇ 4 Pa and the pressure is adjusted to about 0.1 to 10 Pa by introducing a sputtering gas thereafter.
  • a known gas such as argon is used as the sputtering gas, and a gas such as oxygen is further added depending on the purpose.
  • the shape and material of the vacuum chamber 10 are not particularly limited as long as they can withstand such a reduced pressure state, and various types can be used.
  • various devices such as a dry pump, a turbo molecular pump, and a cryocoil are incorporated in the vacuum chamber 10.
  • a free roll 13 for guiding the long resin film 12 and a tension sensor roll 14 for measuring the tension of the long resin film 12 are arranged in this order on the conveyance path from the unwinding roll 11 to the can roll 16. ing.
  • the long resin film 12 fed from the tension sensor roll 14 toward the can roll 16 is adjusted with respect to the peripheral speed of the can roll 16 by a motor-driven front feed roll 15 provided in the vicinity of the can roll 16.
  • the long resin film 12 can be brought into close contact with the outer peripheral surface of the can roll 16.
  • the conveyance path from the can roll 16 to the take-up roll 24 is a motor driven post-feed roll 21 that adjusts the peripheral speed of the can roll 16 and a tension sensor roll that measures the tension of the long resin film 12. 22 and a free roll 23 for guiding the long resin film 12 are arranged in this order.
  • the tension balance of the long resin film 12 is maintained by torque control using a powder clutch or the like.
  • the long resin film 12 is unwound from the unwinding roll 11 and wound around the winding roll 24 by the rotation of the can roll 16 and the motor-driven front feed roll 15 and the rear feed roll 21 that rotate in conjunction with the rotation. It has come to be taken.
  • a film is formed at a position facing a conveyance path defined on the outer peripheral surface of the can roll 16 (that is, a region around which the long resin film 12 is wound on the outer peripheral surface of the can roll 16).
  • Magnetron sputtering cathodes 17, 18, 19, and 20 are provided as means, and gas discharge pipes 25, 26, 27, 28, 29, 30, 31, and 32 for discharging reactive gas are installed in the vicinity thereof.
  • a plate-like target when carrying out the sputtering film formation of the metal absorption layer and the metal layer, a plate-like target can be used as shown in FIG. 5, but when a plate-like target is used, nodules (growth of foreign matter) are formed on the target. May occur. When this becomes a problem, it is preferable to use a cylindrical rotary target that generates no nodules and has high target use efficiency.
  • (2-2-1) A method of releasing reactive gas at a constant flow rate.
  • (2-2-2) A method of releasing reactive gas to maintain a constant pressure.
  • (2-2-3) A method of releasing reactive gas (impedance control) so that the impedance of the sputtering cathode becomes constant.
  • (2-2-4) A method of releasing reactive gas (plasma emission control) so that the plasma intensity of sputtering is constant.
  • the laminated film (metal absorption layer and metal layer) used for the production of the electrode substrate film is etched with an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution.
  • an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution.
  • the metal absorption layer is formed by reactive sputtering using a metal target (metal material) such as a Ni-based alloy, for example, oxygen is added to the sputtering gas argon as a reactive gas to absorb the metal as a black film. A layer is obtained.
  • a metal target metal material
  • oxygen is added to the sputtering gas argon as a reactive gas to absorb the metal as a black film.
  • the etching property of the laminated film (metal absorption layer and metal layer) in the laminate film is examined, as described above, the etching of the metal layer such as copper is easy, but the metal absorption layer is hardly etched. For this reason, in order to improve the etching property of a laminated body film, it is necessary to improve the etching property of a metal absorption layer.
  • the laminate film obtained by performing continuous sputtering film formation on the long resin film using the film forming apparatus of FIG. 5 has different etching rates with the etching solution in the longitudinal direction of the long resin film, and the film formation start side It is confirmed that the etching rate of the laminate film (deposition start side region of the long laminate film) is faster than the deposition end side laminate film (deposition end region of the long laminate film), This phenomenon was presumed to be due to the difference in the etching rate of the metal absorption layer as described above.
  • the graph of FIG. 7 also shows the change in the amount of hydrogen over time.
  • the water decomposes during sputtering, and a part of the film (metal absorption as oxygen and OH) is decomposed.
  • the remaining H atoms are combined and detected as hydrogen molecules (H 2 ).
  • the amount of water measured by the quadrupole mass spectrometer is the remaining amount not used for the film formation reaction.
  • the amount of hydrogen changes in proportion to the amount of water used in the film formation reaction, it is easy to grasp the reaction amount of water.
  • the quadrupole mass spectrometer ionizes gas molecules at the ionization part, accelerates the ions with a potential in a certain direction (the direction of this acceleration potential is Z), and is arranged in parallel with the Z direction.
  • a gas component in the vacuum chamber is detected by separating only ions of a specific mass by a DC voltage applied to a book electrode, a high-frequency AC voltage, and a frequency of the high-frequency AC.
  • the quadrupole mass spectrometer detects the ion current value for ions of a specific mass, it detects the hydrogen amount (content of hydrogen molecules in the vacuum chamber) as the hydrogen ion current value, and the argon amount (Content of argon atoms as sputtering gas in the vacuum chamber) can be detected as an argon ion current value.
  • the chemical composition (the chemical state of Ni) of the metal oxide (metal absorption layer) formed by reactive sputtering using a Ni-based metal target (metal material) is described above according to Non-Patent Document 1.
  • a NiO film is formed, and when moisture is introduced, a NiOOH film is formed.
  • the metal oxide (metal absorption layer) has fine crystal grains, and the presence of the NiOOH which is a hydroxide affects the etching property. Estimated.
  • an alloy target including two or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu is applied.
  • the metal oxide metal absorption layer
  • the present inventor has solved the phenomenon in which the etching rate varies depending on the longitudinal direction of the long resin film by adding water to the reactive gas in order to compensate for the moisture content in the vacuum chamber that decreases during film formation. That is, in the vacuum chamber, water molecules contained in the reactive gas are decomposed into hydrogen and oxygen by sputtering plasma, and a part of the obtained hydrogen is taken into the metal absorption layer as OH.
  • a method for introducing water into the vacuum chamber there are a bubbling method in which a carrier gas is allowed to pass into water, a direct vaporization method in which water is heated and vaporized, and the like.
  • the amount of water added may be determined so as to compensate for the decrease in the amount of water contained in the vacuum chamber over time as described above. It is desirable to control so that the amount of hydrogen in the vacuum chamber taken into the chamber becomes a constant value. Note that the amount of water and the amount of hydrogen contained in the vacuum chamber vary depending on the position of the quadrupole mass spectrometer in the vacuum chamber, the shape of the vacuum chamber, and the like. For this reason, what is necessary is just to set the addition amount of water suitably for every film-forming apparatus.
  • moisture observed by a quadrupole mass spectrometer or the like in a vacuum chamber to which moisture has not been added is released into the vacuum chamber due to release to the atmosphere when the laminated film after film formation is taken out from the vacuum film formation apparatus. It is the moisture in the atmosphere that is adsorbed to the atmosphere.
  • the reactive gas serving as a sputtering atmosphere is argon. It is configured by adding oxygen to the same.
  • oxygen for example, a NiO film (not completely oxidized) can be formed by reactive sputtering using a Ni-based metal target (metal material).
  • the oxygen content of the reactive gas depends on the type of the film forming apparatus and the metal target (metal material), and may be set as appropriate in consideration of optical characteristics such as reflectivity in the metal absorption layer and etching properties with the etching solution 15 volume% or less is desirable.
  • FIG. 7 shows a change in the amount of residual moisture in the vacuum chamber after starting sputtering without supplying moisture into the vacuum chamber. It is confirmed that the residual moisture decreases as the sputtering film formation time elapses.
  • the reason why the moisture decrease immediately after the start of sputtering is fast is considered to be that water molecules adsorbed inside the vacuum chamber are easily desorbed by the plasma and heat generated during sputtering, and the desorbed water molecules are decomposed.
  • the etching progresses fast in the order of the Ni film, the NiOOH film, and the NiO film as described above, depending on the etching solution.
  • the resin film side in the thickness direction of the metal absorption layer be a NiOOH film (not completely oxidized), on the contrary, moisture from the resin film is laminated.
  • importance is attached to the barrier property that does not oxidize the film, it is desirable to make the resin film side in the thickness direction of the metal absorption layer a NiO film (not completely oxidized).
  • reactive gases introduced from the four gas discharge pipes 125, 126, 127, and 128 are selected, and the gas in the vicinity of each gas discharge pipe is selected.
  • the atmospheres 161, 162, 163, and 164 may be obtained.
  • a NiOOH film is easily formed on the resin film side in the thickness direction of the metal absorption layer, and if moisture is introduced from the gas release pipe 128, the thickness direction of the metal absorption layer is increased.
  • a NiO film is easily formed on the resin film side.
  • argon as a sputtering gas and oxygen and water as reactive gases are supplied and exhausted.
  • Electrode substrate film (5-1) The electrode according to the present invention is obtained by etching the laminated film of the laminate film according to the present invention to form a wiring into a thin metal wire having a line width of 20 ⁇ m or less.
  • a substrate film can be obtained.
  • an electrode substrate film as shown in FIG. 4 can be obtained by etching the laminate film of the laminate film shown in FIG.
  • the electrode substrate film as shown in FIG. 4 has a circuit pattern having a mesh structure composed of a transparent substrate 70 made of a resin film and metal laminated thin wires provided on both surfaces of the transparent substrate 70,
  • the manufactured thin thin wires have a line width of 20 ⁇ m or less and counted from the transparent substrate 70 side, the first metal absorption layers 71, 73, the second metal layers 72, 75, 74, 76, and the third The second metal absorption layers 77 and 78 of the layer are configured.
  • the electrode substrate film which concerns on this invention can be used for a touch panel by making the electrode (wiring) pattern of an electrode substrate film into the stripe form or grid
  • the metal laminated thin wires processed into the electrode (wiring) pattern maintain the laminated structure of the laminated film, circuit patterns such as electrodes provided on the transparent substrate even under high luminance illumination Can be provided as an electrode substrate film that is extremely difficult to be visually recognized.
  • a photoresist film is formed on the laminate film surface of the laminate film, exposed and developed so that the photoresist film remains at a position where a wiring pattern is to be formed, and the photoresist film is formed on the laminate film surface.
  • an aqueous solution of ferric chloride or an aqueous solution of cupric chloride can be used as an etching solution for the above chemical etching.
  • Examples 1 to 6 The film forming apparatus (sputtering web coater) shown in FIG. 5 is used, oxygen gas is used as the reactive gas, and the can roll 16 is made of stainless steel having a diameter of 600 mm and a width of 750 mm, and the surface of the roll body is subjected to hard chromium plating.
  • the front feed roll 15 and the rear feed roll 21 are made of stainless steel having a diameter of 150 mm and a width of 750 mm, and hard chrome plating is applied to the surface of the roll body.
  • gas discharge pipes 25, 26, 27, 28, 29, 30, 31, 32 are installed on the upstream side and downstream side of each magnetron sputtering cathode 17, 18, 19, 20, and the magnetron sputtering cathodes 17, 18 are installed. Is attached with a Ni—Cu target for the metal absorption layer, and magnetron sputtering cathodes 19 and 20 with a Cu target for the metal layer.
  • the magnetron sputtering cathodes 17 and 18 in FIG. 5 correspond to the magnetron sputtering cathodes 117 and 118 in FIG. 6, and the gas discharge pipes 25, 26, 27, and 28 in FIG. It corresponds to the pipes 125, 126, 127, and 128.
  • the resin film constituting the transparent substrate was a PET film having a width of 600 mm and a length of 1200 m, and the can roll 16 was controlled to be cooled to 0 ° C.
  • the vacuum chamber 10 was evacuated to 5 Pa using a plurality of dry pumps, and further evacuated to 1 ⁇ 10 ⁇ 4 Pa using a plurality of turbo molecular pumps and cryocoils.
  • the argon gas introduced into the vacuum chamber 10 is dry argon gas that does not pass through water, and is not bubbling argon gas that passes through water.
  • 300 sccm of argon gas is introduce
  • the film was formed.
  • a mixed gas in which 15 sccm is mixed is introduced into the vacuum chamber 10, and power control is performed to obtain a Ni—Cu oxide film thickness of 30 nm for the cathodes 17 and 18 shown in FIG. 5 (magnetron sputtering cathodes 117 and 118 in FIG. 6).
  • the moisture pressure was controlled by the mixing ratio of bubbling argon gas and argon gas. The moisture pressure was adjusted so that the (H 2 / Ar) ratio measured by a quadrupole mass spectrometer provided in the vacuum chamber 10 was constant.
  • argon gas which is a sputtering gas
  • the content of water contained in the reactive gas may be set to a certain amount of offset in consideration of the reflectivity and etching property of the metal absorption layer to be formed.
  • Examples 1 to 6 each composed of a transparent substrate made of a long PET film and a laminated film made of a metal absorption layer that is a Ni—Cu oxide film and a metal layer that is a Cu film provided on the transparent substrate.
  • the laminated body film which concerns on was manufactured.
  • Example 1 it is abbreviated as Example 1 except that water was not introduced from the gas discharge pipes 125 and 126 of the magnetron sputtering first cathode 117 and the gas discharge pipes 127 and 128 of the magnetron sputtering second cathode 118.
  • the comparison was made in the same way and composed of a transparent substrate made of a long PET film, and a laminated film made of a metal absorption layer which is a Ni—Cu oxide film and a metal layer which is a Cu film provided on the transparent substrate.
  • a laminate film according to Example 1 was produced.
  • Laminate films according to Examples 1 to 6 and Comparative Example 1 Laminate film comprising a laminate film composed of a first metal absorption layer and a second copper layer counted from the transparent substrate side
  • Samples were sampled at positions of 100 m and 500 m from the start of film formation, and the spectral reflection characteristics and etching properties of each laminate film were evaluated.
  • the spectral reflection characteristic of the metal absorption layer which is the 1st layer was performed using the self-recording spectrophotometer through the transparent substrate.
  • the said laminated film (a metal absorption layer and a copper layer) was chemically etched using ferric chloride aqueous solution as an etching liquid.
  • the etching property was evaluated according to the following criteria with a superiority mark ( ⁇ , x). “ ⁇ ”: Etching residue cannot be confirmed by visual observation, and is practical. "X”: The etching residue can be confirmed over a wide range by visual observation. (4) The evaluation results are shown in Table 1 below.
  • Example 2 In Example 1 (hydrogen partial pressure: 0.022 Pa), Example 3 (hydrogen partial pressure: 0.066 Pa) and Example 5 (hydrogen partial pressure: 0.004 Pa) in which the oxygen flow rate is 15 sccm Although the superiority or inferiority in the etching property is not confirmed, it is confirmed that the reflectance is lower when the hydrogen partial pressure is higher (in Example 3 where the hydrogen partial pressure is 0.066 Pa, the reflectance is 21%, In Example 1 where the hydrogen partial pressure is 0.022 Pa, the reflectance is 23%, and in Example 5 where the hydrogen partial pressure is 0.004 Pa, the reflectance is 24%.
  • Example 2 oxygen flow rate: 13 sccm
  • Example 4 oxygen flow rate: 16 sccm
  • Example 5 oxygen flow rate: 15 sccm
  • the higher the oxygen flow rate the lower the value of the reflectivity.
  • the oxygen flow rate is 16 sccm
  • the reflectivity is 22%
  • Example 5 the oxygen flow rate is 15 sccm
  • the reflectivity is confirmed. 24%
  • Example 2 where the oxygen flow rate is 13 sccm, the reflectance is 28%).
  • the laminate film according to the present invention is excellent in etching property, and the electrodes of the electrode substrate film according to the present invention produced using the laminate film are difficult to be seen even under high brightness illumination, the FPD (flat panel) Display) Has industrial potential for use as a “touch panel” installed on the surface.

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WO2017130867A1 (ja) * 2016-01-29 2017-08-03 住友金属鉱山株式会社 導電性基板
JP2017223831A (ja) * 2016-06-15 2017-12-21 住友金属鉱山株式会社 電極基板フィルム及びその製造方法
JP2018083976A (ja) * 2016-11-25 2018-05-31 住友金属鉱山株式会社 成膜方法と積層体フィルムの製造方法およびスパッタリング成膜装置

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WO2016175130A1 (ja) * 2015-04-28 2016-11-03 住友金属鉱山株式会社 導電性基板
WO2017130867A1 (ja) * 2016-01-29 2017-08-03 住友金属鉱山株式会社 導電性基板
JPWO2017130867A1 (ja) * 2016-01-29 2018-11-22 住友金属鉱山株式会社 導電性基板
JP2017223831A (ja) * 2016-06-15 2017-12-21 住友金属鉱山株式会社 電極基板フィルム及びその製造方法
JP2018083976A (ja) * 2016-11-25 2018-05-31 住友金属鉱山株式会社 成膜方法と積層体フィルムの製造方法およびスパッタリング成膜装置

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