TW201630720A - Layered-body film, electrode substrate film, and method for manufacturing said films - Google Patents

Abstract

To provide: a layered-body film and an electrode substrate film having exceptional etchability, in which an etched circuit pattern is difficult to see under high-intensity lighting; and a method for manufacturing these films. Provided is a layered-body film configured of a transparent substrate 60 comprising a plastic film, and a layered film provided on at least one surface of the transparent substrate, wherein the layered-body film is characterized in that: the layered film has metal absorption layers 61, 63 of a first layer of metal layers (62, 65), (64, 66) of a second layer, as counted from the transparent substrate side; and the metal absorption layers are formed by a reactive sputtering method involving the use of an oxygen-containing reactive gas and a metal target comprising elemental Ni or an alloy including two or more elements selected from Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, the reactive gas containing water.

Description

Laminate film and electrode substrate film and manufacturing method thereof

The present invention relates to a laminate film having a transparent substrate including a resin film and a laminate film, and an electrode substrate film which is produced by etching a laminate film of the laminate film and used for a touch panel or the like, and particularly relates to etching properties. A multilayer thin film and an electrode substrate thin film which are excellent in the etching process and are formed in a high-intensity illumination, and a method of manufacturing the same.

In recent years, "touch panels" installed on the surface of flat panel displays (FPDs) such as mobile phones, mobile electronic document devices, vending machines, and car navigation are beginning to spread.

The above-mentioned "touch panel" is roughly classified into a resistive type and an electrostatic capacity type. The main part of the "resistive touch panel" is composed of a transparent substrate including a resin film, an X coordinate (or Y coordinate) detection electrode sheet and a Y coordinate (or X coordinate) detection electrode sheet provided on the substrate; And an insulator spacer disposed between the sheets. Further, the X coordinate detecting electrode piece and the Y coordinate detecting electrode piece are separated by a space, and when pressed by a pen or the like, the two coordinate detecting electrode pieces are electrically contacted to each other to know the position touched by the pen ( The X coordinate and the Y coordinate), as long as the pen is moved, the coordinates can be recognized each time, and the text can be input. another In the "static capacitance type touch panel", an X-coordinate (or Y-coordinate) detection electrode sheet and a Y-coordinate (or X-coordinate) detection electrode sheet are laminated via an insulating sheet, and glass is disposed on the electrode sheets. The construction of the insulator. Further, when the finger is brought close to the insulator such as glass, the capacitance of the X coordinate detecting electrode and the Y coordinate detecting electrode in the vicinity thereof is changed, so that position detection can be performed.

In addition, as a conductive material constituting a circuit pattern such as an electrode, a transparent conductive film such as ITO (indium oxide-tin oxide) has been widely used (see Patent Document 1). In addition, with the increase in size of the touch panel, metal thin wires (metal films) disclosed in the mesh structures of Patent Document 2 and Patent Document 3 have been used.

When the transparent conductive film and the metal thin wire (metal film) are compared, the transparent conductive film has an advantage that the circuit pattern such as an electrode is hardly recognized because of excellent permeability in a visible wavelength region, but the resistance value is higher than that of metal. Since the thin wire (metal film) is high, it has a disadvantage that it is not suitable for an increase in the size of the touch panel or an increase in the response rate. On the other hand, since the metal thin wire (metal film) has a low resistance value, it is suitable for increasing the size of the touch panel or increasing the response rate. However, since the reflectance in the visible wavelength region is high, for example, even if it is processed into fine particles, The mesh structure also sees the circuit pattern under high-intensity illumination, which reduces the value of the product.

Therefore, in order to exhibit the characteristics of the metal thin wire (metal film) having a low electric resistance value, it is proposed to present a metal absorbing layer (referred to as a blackened film) containing a metal oxide in a transparent substrate including a resin film and a metal thin wire. Between (metal film) (refer to Patent Document 4 and Patent Document 5), A method of reducing reflection of a metal thin wire (metal film) observed on the transparent substrate side.

Further, from the viewpoint of the film forming efficiency of the metal oxide, the metal absorbing layer containing the metal oxide is usually continuously formed by reactive sputtering using a metal target (metal material) and a reactive gas. The film is formed on the surface of the elongated resin film, and the metal layer is continuously formed on the metal absorption layer of the film formed by sputtering or the like using a metal target (metal material) such as copper. A laminate film for the production of a film.

Further, the electrode substrate film used in a touch panel or the like is a laminated film including a transparent substrate including a resin film and a laminated film including a metal absorbing layer and a metal layer provided on the substrate. An etching solution such as a copper chloride aqueous solution or an aqueous ferric chloride solution is subjected to an etching treatment, and the laminated film (metal absorbing layer and metal layer) of the laminated thin film is processed into a circuit pattern such as an electrode.

Therefore, the laminated thin film used for the production of the electrode substrate film is required to have a property that the buildup film (the metal absorption layer and the metal layer) is easily etched by an etching solution such as a copper chloride aqueous solution or a ferric chloride aqueous solution, and an etched process. A circuit pattern such as an electrode is difficult to be recognized under high-intensity illumination.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-151358 (refer to claim 2)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-018194 (refer to claim 1)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2013-069261 (refer to paragraph 0004)

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2014-142462 (refer to claim 5, paragraph 0038)

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2013-225276 (refer to claim 1 and fall 0041)

[Non-patent literature]

[Non-Patent Document 1] J. Vac. Soc. Jpn. Vol. 53, No. 9, (2010), p515-520

However, a metal absorbing layer containing a metal oxide is continuously formed on the surface of the elongated resin film by using a metal target (metal material) such as a Ni-based alloy or a reactive sputtering of an oxygen-containing reactive gas. When a laminate film obtained by continuously forming a metal layer on the metal absorption layer by sputtering or the like using a metal target (metal material) such as copper is used to produce an electrode substrate film, the following results are produced. problem.

In other words, when the laminated film (metal absorbing layer and metal layer) of the laminated thin film is etched to form an electrode substrate film, the film forming start end side of the metal absorbing layer is formed at the initial stage of film formation. The laminated film (the film forming start end side region of the long laminated film) is applied to the end of the film forming end of the metal absorbing layer at the end of film formation (the end of the film forming end of the elongated laminated film) Area) There is a problem that the etching property is deteriorated, and there is a problem that the processing precision of the circuit pattern in the electrode substrate film due to this is unstable.

The present invention has been made in view of such a problem, and an object of the present invention is to provide a laminate film and an electrode substrate film which are excellent in etchability and which are difficult to be recognized even under high-luminance illumination. At the same time, a method of manufacturing each of the laminate film and the electrode substrate film is provided.

Then, the inventors of the present invention investigated the etchability of the laminate film on the end of the film formation end as compared with the etchability of the laminate film on the film formation start end side, and reviewed the improvement measures.

When the etchability of the metal absorbing layer and the metal layer of the laminated film constituting the laminated film is examined, it is confirmed that a metal target (metal material) such as a Ni-based alloy and an oxygen-containing reactive gas are used. The metal absorbing layer formed by reactive sputtering or the like is less likely to be a copper chloride aqueous solution, a ferric chloride aqueous solution or the like than a metal layer formed by sputtering using a metal target (metal material) such as copper. The etching solution is etched. From this, it is predicted that the metal absorbing layer containing the metal oxide in the metal absorbing layer and the metal layer of the laminated film constituting the laminated film is related to the etching property of the film at the end of the film forming end. In view of this, the chemical composition of a metal oxide (metal absorbing layer) formed by reactive sputtering such as a metal target (metal material) such as a Ni-based alloy is used for literature investigation, and Non-Patent Document 1 discloses that In the case of reactive sputtering using a Ni-based metal target (metal material), when oxygen is introduced into the vacuum chamber as a reactive gas, the metal oxide becomes a NiO film, and when water is introduced, In the case of a reactive gas, the metal oxide becomes a NiOOH film.

Therefore, according to the description of Non-Patent Document 1, the Ni film is formed by sputtering using a Ni-based metal target (metal material), and further, the reactivity of the Ni-based metal target (metal material) is used. When the etching effect of the etching liquid such as the aqueous solution of copper chloride or the aqueous solution of ferric chloride was investigated by sputtering, the film was observed, and it was confirmed that the film having a high etching rate was sequentially Ni film. , NiOOH film, NiO film. From this, it is understood that a part of the metal oxide formed in the laminate film at the film formation start end side is a NiOOH film which is easily etched (the Ni film having an etching property superior to the NiOOH film is not a metal oxide, and does not correspond to a metal. In the absorption layer, the majority of the metal oxide formed in the laminate film at the end of the film formation is a NiO film (it is difficult to be etched than the NiOOH film), and it is predicted that the above-mentioned reactivity is caused by the above-mentioned reactivity. A change with time in the film formation environment when a metal oxide (metal absorbing layer) is formed by sputtering or the like (change in residual moisture in the vacuum chamber with time).

Under the investigation of this technique, when the change of the moisture content in the vacuum chamber was measured with time using a quadrupole mass spectrometer, as shown in Fig. 7, it was confirmed that the initial phase of film formation with the metal oxide (metal absorbing layer) was observed. In comparison, at the end of the film formation, the amount of water in the vacuum chamber is significantly reduced.

In addition, it has been confirmed that other alloys containing two or more elements selected from Ti, Cu, Al, V, W, Ta, etc., are used instead of the Ni-based target such as the Ni-based alloy described above. In the case of the target material, the etching property of the laminated body film at the end of the film formation is deteriorated as the moisture content in the vacuum chamber is reduced, compared to the laminated film on the film formation start end side.

The present invention has been completed by such investigation and technical analysis, and a metal oxide is formed by reactive sputtering using a metal target (metal material) such as a Ni-based alloy and an oxygen-containing reactive gas. In the case of the metal absorbing layer, the reactive gas is made to contain water, and the content of the hydrogen molecules measured by the quadrupole mass spectrometer already installed in the film forming chamber and the content of the argon atoms belonging to the sputtering gas are respectively the hydrogen ion current values. And the argon ion current value is detected, and the ratio (H ₂ /Ar) of the content of the hydrogen molecule and the content of the argon atom detected in the form of the ion current value is constant, and is set to be included in the reactive gas. The content of water is increased by the amount of the residual moisture in the film forming chamber, and the metal oxide (metal absorbing layer) is formed, thereby improving the etching property of the laminated film in the laminated film.

In the first aspect of the invention, the laminate film is a laminate film comprising a transparent substrate comprising a resin film and a laminate film provided on at least one surface of the transparent substrate, and is characterized in that:

The laminated film has a metal absorbing layer which is the first layer from the transparent substrate side and a metal layer of the second layer, and the metal absorbing layer is formed by a reaction film forming method using a metal material and an oxygen-containing reactive gas. The metal material is composed of an alloy containing a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and the above reactive gas Contains water.

The laminated film according to the first aspect of the invention, wherein the metal layer has a film thickness of 50 nm or more and 5000 nm or less.

According to a third aspect of the invention, the laminated film of the first aspect of the invention, wherein the laminated film has a second metal absorbing layer which is a third layer from a transparent substrate side, and the second metal absorbing layer is formed by using a metal material and oxygen Reactivity The gas is formed by a reaction film formation method, and the metal material is composed of a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy is composed of the above-mentioned reactive gas containing water.

According to a fourth aspect of the invention, the laminated body film according to the first aspect or the third aspect of the invention, wherein the alloy is one selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu The above elements are composed of a Ni-based alloy.

According to a fifth aspect of the invention, there is provided an electrode substrate film comprising: a transparent substrate including a resin film; and an electrode substrate film including a circuit pattern of a mesh structure provided on at least one surface of the transparent substrate; for: The metal laminated thin wire has a line width of 20 μm or less, has a metal absorbing layer of the first layer from the transparent substrate side, and a metal layer of the second layer, and the metal absorbing layer is made of a metal material and oxygen-containing reactivity. The gas is formed by a reaction film formation method, and the metal material is composed of a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy is composed of the above-mentioned reactive gas containing water.

The electrode substrate film according to the fifth aspect of the invention, wherein the metal layer has a film thickness of 50 nm or more and 5000 nm or less.

The electrode substrate film according to the fifth aspect of the invention, wherein the metal laminated thin wire has a second metal absorbing layer which is a third layer from a transparent substrate side, and the second metal absorbing layer is formed by using a metal material and The oxygen-containing reactive gas is formed by a reaction film forming method, and the metal material is composed of a Ni-containing monomer or selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag. An alloy of two or more elements of Mo and Cu, and the reactive gas contains water.

The electrode substrate film according to the fifth aspect of the invention, wherein the alloy is one or more selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The element is made of a Ni-based alloy.

According to a ninth aspect of the invention, there is provided a method for producing a laminate film comprising a transparent substrate comprising a resin film and a laminate film provided on at least one surface of the transparent substrate, wherein the method comprises the steps of: for: have: In the first step, a metal absorption layer which is the first layer from the transparent substrate side of the laminate film is formed by a reaction film formation method using a metal material and an oxygen-containing reactive gas, and the metal material is composed of a Ni-containing single layer. An alloy or an alloy of two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu; In the second step, a metal layer which is calculated as a second layer from the transparent substrate side of the laminated film is formed by a film forming method using a metal material; Further, the reactive gas in the first step described above contains water.

According to a ninth aspect of the invention, there is provided a method for producing a laminate film according to the ninth aspect of the invention, comprising the third step of forming a transparent substrate comprising the laminate film by a reaction film formation method using a metal material and an oxygen-containing reactive gas; The side is counted as the second metal absorbing layer of the third layer, and the metal material is composed of a Ni-containing monomer or two selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy of the above elements is composed, and the reactive gas in the third step contains water.

The method of producing a laminate film according to the ninth aspect or the tenth aspect of the invention, wherein the alloy is added with one selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu A Ni-based alloy of the above elements is composed of a plurality of elements.

The method of producing a laminated film according to the ninth aspect or the tenth aspect of the present invention, wherein the content of water contained in the reactive gas is set to supplement residual moisture in the film forming chambers of the first step and the third step The amount of reduction in amount.

According to a thirteenth aspect of the invention, in the method for producing a laminate film according to the twelfth aspect of the invention, the ratio of the content of the hydrogen molecules measured by the gas component detecting means provided in the film forming chamber to the content of the argon atoms belonging to the sputtering gas ( H ₂ /Ar) is a constant method of setting the content of water contained in the reactive gas to supplement the amount of reduction in residual moisture in the film forming chambers in the first step and the third step.

According to a thirteenth aspect of the invention, in the method for producing a laminate film according to the thirteenth aspect of the invention, the gas component detecting means is configured by a quadrupole mass spectrometer, and the content of the hydrogen molecule measured by the quadrupole mass spectrometer is detected as a hydrogen ion current value, and The content of argon atoms measured by the quadrupole mass spectrometer was detected as an argon ion current value.

According to a fifteenth aspect of the invention, there is provided a method of producing an electrode substrate film comprising: a transparent substrate including a resin film; and a circuit pattern including a mesh structure of a metal laminated thin wire provided on at least one surface of the transparent substrate A method for producing an electrode substrate film, characterized in that: The laminated film of the laminated thin film according to any one of the first invention to the third invention is subjected to a chemical etching treatment to form the gold having a line width of 20 μm or less. The laminated thin wires are processed for wiring.

According to a sixteenth aspect of the invention, there is provided a method for producing an electrode substrate film, comprising: a transparent substrate including a resin film; and an electrode substrate film including a circuit pattern of a mesh structure provided on at least one surface of the transparent substrate; Method, characterized by: The laminated film of the laminated thin film of the fourth invention is subjected to a chemical etching treatment, and the metal laminated thin wires having a line width of 20 μm or less are subjected to wiring processing.

A laminated film of the present invention comprising a transparent substrate comprising a resin film and a laminated film provided on at least one surface of the transparent substrate, wherein the laminated film has a metal absorption as a first layer from a transparent substrate side. a layer and a metal layer of the second layer, and the metal absorbing layer is formed by a reaction film forming method using a metal material and an oxygen-containing reactive gas, the metal material being composed of a Ni monomer or selected from Ni, Ti An alloy of two or more elements of Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and the reactive gas contains water.

In the laminate film of the present invention, the metal oxide (metal absorbing layer) of the laminated film is formed while the water is contained in the reactive gas to replenish the amount of water in the vacuum chamber. Since the film is formed, it is possible to avoid the problem that the etching property of the laminate film on the end of the film formation is not as good as the etching property of the laminate film on the film formation start end side.

Therefore, it is possible to provide a thin layer of a circuit pattern which is excellent in etching property and which is formed by etching treatment and which is difficult to recognize under high-intensity illumination. The effect of the film and electrode substrate film.

10‧‧‧vacuum chamber

11‧‧‧Rolling roll

12‧‧‧Long resin film

13‧‧‧Free roll

14‧‧‧Tensance roller

15‧‧‧Advance roll

16‧‧‧canned rolls

17‧‧‧Magnetron Sputtered Cathode

18‧‧‧Magnetron Sputtered Cathode

19‧‧‧Magnetron Sputtered Cathode

20‧‧‧Magnetron Sputtered Cathode

21‧‧‧Back feed roller

22‧‧‧Tensance roller

23‧‧‧Free roll

24‧‧‧Winding roller

25‧‧‧ gas discharge pipe

26‧‧‧ gas discharge pipe

27‧‧‧ gas discharge pipe

28‧‧‧ gas discharge pipe

29‧‧‧ gas discharge pipe

30‧‧‧ gas discharge pipe

31‧‧‧ gas discharge pipe

32‧‧‧ gas discharge pipe

40‧‧‧Resin film (transparent substrate)

41‧‧‧Metal absorption layer

42‧‧‧metal layer (copper layer)

43‧‧‧Metal absorption layer

44‧‧‧metal layer (copper layer)

50‧‧‧Resin film (transparent substrate)

51‧‧‧Metal absorption layer

52‧‧‧Metal layer (copper layer) formed by dry film formation

53‧‧‧Metal absorption layer

54‧‧‧Metal layer (copper layer) formed by dry film formation

55‧‧‧Metal layer (copper layer) formed by wet film formation

56‧‧‧Metal layer (copper layer) formed by wet film formation

60‧‧‧Resin film (transparent substrate)

61‧‧‧Metal absorption layer

62‧‧‧Metal layer (copper layer) formed by dry film formation

63‧‧‧Metal absorption layer

64‧‧‧Metal layer (copper layer) formed by dry film formation

65‧‧‧Metal layer (copper layer) formed by wet film formation

66‧‧‧Metal layer (copper layer) formed by wet film formation

67‧‧‧2nd metal absorbing layer

68‧‧‧2nd metal absorbing layer

70‧‧‧Resin film (transparent substrate)

71‧‧‧Metal absorption layer

72‧‧‧Metal layer (copper layer) formed by dry film formation

73‧‧‧Metal absorption layer

74‧‧‧Metal layer (copper layer) formed by dry film formation

75‧‧‧Metal layer (copper layer) formed by wet film formation

76‧‧‧Metal layer (copper layer) formed by wet film formation

77‧‧‧2nd metal absorbing layer

78‧‧‧2nd metal absorbing layer

116‧‧‧canned roller

117‧‧‧Magnetron sputtering first cathode

118‧‧‧Magnetron sputtering second cathode

125‧‧‧ gas discharge pipe

126‧‧‧ gas discharge pipe

127‧‧‧ gas discharge pipe

128‧‧‧ gas discharge pipe

161‧‧‧ gas environment

162‧‧‧ gas environment

163‧‧‧ gas environment

164‧‧‧ gas environment

1 is a schematic cross-sectional explanatory view of a laminate film of the present invention having a metal absorbing layer of a first layer and a metal layer of a second layer from both sides of a transparent substrate including a resin film.

2 is a metal layer having a metal absorbing layer and a second layer which are the first layer from the transparent substrate side on both surfaces of the transparent substrate including the resin film, and the metal layer is a dry film forming method and a wet film forming method. A schematic cross-sectional view of the laminated film of the present invention formed.

3 is a view showing a metal absorbing layer which is a first layer from a transparent substrate side, a metal layer of a second layer, and a second metal absorbing layer of a third layer on both surfaces of a transparent substrate including a resin film, and the metal layer is formed by A schematic cross-sectional view of a laminate film of the present invention formed by a dry film formation method and a wet film formation method.

4 is a schematic cross-sectional explanatory view of an electrode substrate film of the present invention in which metal laminated wires are formed on both surfaces of a transparent substrate including a resin film.

Fig. 5 is an explanatory view of a film forming apparatus (sputter web coater) which performs a vacuum film forming method for forming a metal absorbing layer and a metal layer on a transparent substrate including a resin film.

Fig. 6 is a partial enlarged view of the film forming apparatus (sputter web coater) shown in Fig. 5.

Fig. 7 is a graph showing changes in the amount of water and the amount of hydrogen in the vacuum chamber as a function of time.

[Formation of the Invention]

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

(1) laminated film

The first laminate film of the present invention comprises a transparent substrate including a resin film and a laminated film provided on at least one surface of the transparent substrate, wherein the laminated film has a first thickness from the transparent substrate side. a metal absorbing layer of the layer and a metal layer of the second layer, and the metal absorbing layer is formed by a reaction film forming method using a metal material and an oxygen-containing reactive gas, the metal material being composed of a Ni monomer, or An alloy composed of two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and the reactive gas contains water, and the second laminate of the present invention The bulk film is characterized in that the laminated film has a second metal absorbing layer which is a third layer from the transparent substrate side, and the second metal absorbing layer is made of a metal material. Formed by a reaction film formation method with an oxygen-containing reactive gas, the metal material is composed of a Ni-containing monomer or selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. An alloy composed of two or more elements, and the above reactive gas contains Water.

(1-1) First laminate film

As shown in FIG. 1, the first laminate film is made of a transparent substrate 40 including a resin film, and metal absorbing layers 41 and 43 formed on both surfaces of the transparent substrate 40 by a dry film formation method (dry plating method). Metal layer 42 44.

Further, 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).

That is, as shown in FIG. 2, a transparent substrate 50 including a resin film; a metal absorption of 15 nm to 30 nm formed on both surfaces of the transparent substrate 50 by a dry film formation method (dry plating method) Layers 51, 53; metal layers 52, 54 formed on the metal absorbing layers 51, 53 by a dry film forming method (dry plating method); and formed by a wet film forming method (wet plating method) The metal layers 55, 56 on the metal layers 52, 54 are formed.

(1-2) Second laminate film

Next, the second laminate film is formed on the metal layer of the laminate film on the premise that the first laminate film shown in FIG. 2 is formed.

That is, as shown in FIG. 3, the transparent substrate 60 including the resin film; the metal absorbing layer 61 having a thickness of 15 nm to 30 nm formed on both surfaces of the transparent substrate 60 by a dry film formation method (dry plating method), 63; metal layers 62, 64 formed on the metal absorbing layers 61, 63 by a dry film forming method (dry plating method); formed on the metal layer by a wet film forming method (wet plating method) The metal layers 65 and 66 on 62 and 64; and the second metal absorption layers 67 and 68 having a thickness of 15 nm to 30 nm formed on the metal layers 65 and 66 by a dry film formation method (dry plating method). .

Here, in the second laminated film shown in FIG. 3, the metal absorbing layer 61 and the second metal absorbing layer 67 are formed on both surfaces of the metal layers indicated by the element numerals 62 and 65, and the element symbols 64 and 66 are formed. A metal absorbing layer 63 and a second metal absorbing layer 68 are formed on both sides of the metal layer shown, which is In order to incorporate the electrode substrate film obtained by using the laminated thin film into the touch panel, the circuit pattern including the mesh structure of the metal laminated thin wires is reflected and cannot be seen.

Further, even when a first laminate film having a metal layer formed on one surface of a transparent substrate including a resin film and a metal layer is formed on the metal absorption layer to form an electrode substrate film, it is possible to prevent the film from being formed. The transparent substrate recognizes the above circuit pattern.

(1-3) Materials constituting the metal absorbing layer (metal material)

The metal absorbing layer is formed by a reaction film forming method using a metal material and an oxygen-containing reactive gas, and the metal material is composed of a Ni-containing monomer or selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si. An alloy of two or more elements of Cr, Ag, Mo, and Cu. In addition, as the alloy, a Ni-based alloy to which one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added can be widely used as the Ni-based alloy. Preferably, it is a Ni-Cu alloy. Further, when the oxidation of the metal oxide constituting the metal absorbing layer is excessively performed, the metal absorbing layer becomes transparent, and therefore it is necessary to set the oxidation level to the extent that the blackening film is formed. The above reaction film formation methods include magnetron sputtering, ion beam sputtering, vacuum evaporation, ion plating, CVD, and the like. Further, the optical constants (refractive index, extinction coefficient) of the respective wavelengths of the metal absorbing layer are largely affected by the degree of reaction, that is, the degree of oxidation, and are not determined only by the metal material containing the Ni-based alloy.

(1-4) The constituent material of the metal layer (metal material)

The constituent material (metal material) of the metal layer is not particularly limited as long as it has a low electrical resistance value, and examples thereof include: a Cu-based alloy or a Cu-based alloy to which one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, and Ag are added; or an Ag monomer or an additive selected from the group consisting of Ti and Al An Ag-based alloy of one or more elements of V, W, Ta, Si, Cr, and Cu is particularly preferable from the viewpoint of workability of a circuit pattern or a resistance value.

Further, the film thickness of the metal layer depends on the electrical characteristics and is not determined by the optical elements, but is usually set to a thickness at which the transmitted light cannot be measured.

Further, the desired film thickness of the metal layer is preferably 50 nm or more, and more preferably 60 nm or more from the viewpoint of electric resistance. On the other hand, from the viewpoint of the workability of processing the metal layer into the wiring pattern, it is preferably 5 μm (5000 nm) or less, more preferably 3 μm (3000 nm) or less.

(1-5) Resin film constituting a transparent substrate

The material of the resin film to be applied to the above laminated film is not particularly limited, and specific examples thereof include self-polymerization of ethylene terephthalate (PET), polyether oxime (PES), and polyarylate ( a monomer of a resin film of a resin material of PAR), polycarbonate (PC), polyolefin (PO), triacetyl cellulose (TAC), and norbornene, or a resin selected from the above resin materials A composite of a film monomer and an acrylic organic film covering one or both sides of the monomer. In particular, the norbornene resin material is exemplified by ZEONOR (trade name) of Japan ZEON Co., Ltd., ARTON (trade name) of JSR Corporation, and the like.

In addition, since the electrode substrate film produced by using the laminate film of 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. to make.

(2) A film forming apparatus that performs a reaction film forming method

(2-1) Sputtering web coating machine

The film forming apparatus will be described by taking a sputtering method as an example of a film forming method.

Further, this film forming apparatus is called a sputter web coater and is used for continuous and efficient film forming treatment on the surface of an elongated resin film conveyed by a roll-to-roll method. The situation. .

Specifically, a film forming apparatus (sputter web coater) of an elongated resin film conveyed by a roll-to-roll method is provided in the vacuum chamber 10 as shown in FIG. 5, and is attached to the take-up roll 11 The rolled elongated resin film 12 is wound up by a take-up roll 24 after performing a predetermined film forming process. In the middle of the conveyance path of the take-up roll 12 to the take-up roll 24, a can roll 16 that is rotationally driven by a motor is disposed. The temperature-adjusted refrigerant outside the vacuum chamber 10 is circulated inside the can roller 16.

In the vacuum chamber 10, in order to perform sputtering deposition, pressure reduction up to a pressure of about 10 ^-4 Pa and pressure adjustment of about 0.1 to 10 Pa formed by introduction of a subsequent sputtering gas are performed. A well-known gas such as argon is used in the sputtering gas system, and a gas such as oxygen may be 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 configurations can be used. Further, in order to reduce the pressure in the vacuum chamber 10 and maintain this state, various devices (not shown) such as a dry pump, a turbo molecular pump, and a cryocoil are attached to the vacuum chamber 10.

The conveying path of the take-up roll 11 to the can-shaped roll 16 is sequentially arranged The free roller 13 for guiding the elongated resin film 12 and the tension sensing roller 14 for measuring the tension of the elongated resin film 12 are placed. Further, the elongated resin film 12 which is fed from the tension sensing roller 14 toward the can roller 16 is subjected to the peripheral speed of the can roller 16 by the motor-driven forward roller 15 provided in the vicinity of the can roller 16. By this adjustment, the elongated resin film 12 can be adhered to the outer circumferential surface of the can roller 16.

In the same manner as described above, the transport path of the can roller 16 to the take-up roller 24 is sequentially arranged, and the motor-driven rear feed roller 21 for adjusting the peripheral speed of the can roller 16 is arranged in order to measure the tension of the elongated resin film 12. The tension sensing roller 22 and the free roller 23 that guides the elongated resin film 12.

In the winding roller 11 and the winding roller 24, the tension balance of the elongated resin film 12 is maintained by torque control by a powder clutch or the like. Further, the elongated resin film 12 is taken up from the take-up roll 11 and taken up to the take-up roll 24 by the rotation of the can roller 16 and the motor-driven feed roller 15 and the rear feed roller 21 which are rotated in conjunction therewith. .

In the vicinity of the can roller 16, the conveyance path (i.e., the region of the elongated resin film 12 wound in the outer circumferential surface of the can roller 16) is opposed to the conveyance path defined on the outer circumferential surface of the can roller 16. The magnetron sputtering cathodes 17, 18, 19, and 20 as film forming means are disposed at positions, and gas discharge pipes 25, 26, 27, 28, 29, 30 for emitting a reactive gas are disposed in the vicinity thereof. 31, 32.

Further, when the metal absorbing layer and the metal layer are sputter-deposited, as shown in FIG. 5, a plate-shaped target can be used. However, when a plate-shaped target is used, a protrusion may be generated on the target. (nodule) (the growth of foreign bodies). When this becomes a problem, it is preferred that the use does not produce protrusions and A cylindrical rotating target with high efficiency of use of the target.

(2-2) Reactive sputtering

In the case where an oxide target is applied in order to form a metal absorption layer containing a metal oxide, the film formation rate is slow and it is not suitable for mass production. For this reason, a reaction film formation method using a metal target (metal material) such as a Ni-based alloy which can form a film at a high speed, and a reactive sputtering which is introduced while controlling the oxygen-containing reactive gas is used.

Further, the following four methods are known for the method of controlling the reactive gas.

(2-2-1) A method of releasing a reactive gas at a constant flow rate.

(2-2-2) A method of releasing a reactive gas in such a manner as to maintain a constant pressure.

(2-2-3) A method of releasing a reactive gas (impedance control) so that the impedance of the sputtering cathode is constant.

(2-2-4) A method of releasing a reactive gas (plasma emission control) in such a manner that the intensity of the plasma of the sputtering is constant.

(3) Film formation of the metal absorption layer

The laminated film used for the production of the electrode substrate film is required to be characterized in that the buildup film (metal absorbing layer and metal layer) is easily etched by an etching solution such as a copper chloride aqueous solution or a ferric chloride aqueous solution, and an electrode which is etched. The circuit pattern is difficult to identify under high-intensity illumination.

When the metal absorbing layer is formed by reactive sputtering using a metal target (metal material) such as a Ni-based alloy, the argon-added oxygen of the sputtering gas is used as a reactive gas to obtain a metal as a black film. Absorbing layer.

Then, when the etching property of the laminated film (metal absorbing layer and metal layer) in the laminated film is investigated, as described above, etching of a metal layer such as copper is easy, but the metal absorbing layer is difficult to be etched. Therefore, in order to improve the etching property of the laminated film, it is necessary to improve the etching property of the metal absorbing layer.

In addition, the laminate film obtained by continuous sputtering film formation on the elongated resin film using the film forming apparatus of FIG. 5 was confirmed to be carried out by the etching liquid in the longitudinal direction of the elongated resin film. The etching rate is different from the etching rate at the film forming start end side laminated body film (the film forming start end side region of the long laminated film), and the film forming end film side film forming film (the film forming end end side of the elongated laminated film) The region is fast, and this phenomenon can be inferred as described above because the etching rate of the metal absorbing layer is different.

On the other hand, in a vacuum film forming apparatus in which a long resin film is continuously sputter-deposited by a quadrupole mass spectrometer or the like, the amount of water contained in the vacuum chamber is reduced with time (refer to the graph of FIG. 7). ).

In addition, the graph of Fig. 7 also describes the change of the amount of hydrogen with time. When there is moisture in the vacuum chamber, the water will be decomposed in the sputtering, and a part thereof is captured into the film in the form of oxygen and OH ( The metal absorbing layer), so the remaining H is combined with each other and detected as hydrogen molecules (H ₂ ). In this manner, a part of the moisture in the chamber is used for the film formation reaction by sputtering, so the amount of water measured by the quadrupole mass spectrometer is used for the residual amount of the film formation reaction. On the other hand, since the amount of hydrogen changes in proportion to the amount of water used in the film formation reaction, it is easy to grasp the amount of reaction of water.

However, in the above-described quadrupole mass spectrometer, gas molecules are ionized in the ionization portion, and the ions are accelerated at a potential in a certain direction (the direction of the acceleration potential is Z), and are arranged in parallel with the Z direction by application. The DC voltage of the four electrodes and the high-frequency AC voltage and the frequency of the high-frequency alternating current separate only ions of a specific mass, thereby detecting the gas component in the vacuum chamber. In addition, since the quadrupole mass spectrometer is detected in the form of its ion current value for a specific mass of ions, the amount of hydrogen (the content of hydrogen molecules in the vacuum chamber) can be detected as a hydrogen ion current value, and the amount of argon is measured. (The content of argon atoms of the sputtering gas in the vacuum chamber) is detected as an argon ion current value.

Further, according to Non-Patent Document 1, the chemical composition of the metal oxide (metal absorbing layer) formed by reactive sputtering using a Ni-based metal target (metal material) (chemical state of Ni) As described above, when oxygen is introduced as a reactive gas, it becomes a NiO film, and when water is introduced, it becomes a NiOOH film. Further, in the process in which the inventors of the present invention repeatedly conducted a trial test of the laminated film, it was concluded that the crystal grains of the metal oxide (metal absorbing layer) were fine, and the presence of the above-mentioned NiOOH of the hydroxide caused etchability. influences. In addition, even if the Ni-based metal target is replaced, an alloy target including two or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu is used. In the case of the formed metal oxide (metal absorbing layer), the presence of hydroxide also affects the etchability.

Therefore, the inventor of the present invention supplements the moisture content in the vacuum chamber in the film formation by including water in the reactive gas. The phenomenon that the etching rate differs depending on the longitudinal direction of the elongated resin film is solved. That is, the reason is that in the vacuum chamber, the water molecules contained in the reactive gas are decomposed into hydrogen and oxygen by the sputtered plasma, and a part of the obtained hydrogen is absorbed into the metal in the form of OH. Floor.

Further, a method of introducing water into the vacuum chamber may be a bubbling method in which a carrier gas is passed through water, a direct gasification method in which water is heated and vaporized, and the like.

The amount of water to be added may be set as described above so as to supplement the amount of moisture contained in the vacuum chamber over time, preferably by decomposition reaction of water and being captured in the form of OH. The amount of hydrogen in the vacuum chamber of the membrane (metal absorbing layer) is controlled to be a constant value. In addition, the amount of water and the amount of hydrogen contained in the vacuum chamber It varies depending on the arrangement position of the quadrupole mass spectrometer in the vacuum chamber, the shape of the vacuum chamber, and the like. Therefore, the amount of water to be added may be appropriately set for each film forming apparatus.

In addition, in the vacuum chamber in which no moisture is added, the moisture observed by the quadrupole mass spectrometer or the like is caused by the atmosphere in the vacuum film forming apparatus being taken out from the vacuum film forming apparatus when the film is formed, and is adsorbed to the atmosphere in the vacuum chamber. Moisture in the water.

(4) Introduction of reactive gas in the film forming apparatus

When a metal absorption layer is formed by reactive sputtering such as a metal target (metal material) such as a Ni-based alloy, a reactive gas system which is a sputtering environment is formed by adding oxygen to argon or the like. By adding oxygen, for example, reactive sputtering using a Ni-based metal target (metal material) can be used as a NiO film (not completely oxidized) or the like. The oxygen content of the reactive gas, only Depending on the type of the film forming apparatus or the metal target (metal material), the optical characteristics such as the reflectance of the metal absorbing layer or the etching property of the etching liquid may be appropriately set, and preferably 15% by volume or less. .

In addition, FIG. 7 shows a change in the residual moisture content in the vacuum chamber after the sputtering is started without supplying moisture into the vacuum chamber. It was confirmed that the residual moisture gradually decreased as the sputtering film formation time elapsed. At the beginning of the sputtering, the moisture is rapidly lowered. This is considered to be because the plasma and heat generated during the sputtering cause the water molecules adsorbed inside the vacuum chamber to be easily separated and the separated water molecules to be decomposed.

Next, the periphery of the sputtering cathodes 17, 18 of the film forming apparatus of Fig. 5 is shown in an enlarged view of Fig. 6.

In the case where the metal absorbing layer which is the first layer from the transparent substrate side is formed by using two sputtering cathodes, the reactive gas can be introduced into the four gases for releasing the reactive gas in the vicinity of the sputtering cathode. Tubes 125, 126, 127, 128.

When a Ni-based metal target (metal material) is used, it is also dependent on the etching liquid, and the etching progress rate is as described above, and is, in order, a Ni film, a NiOOH film, or a NiO film. Further, when the etching property is emphasized, it is preferable to form the resin film side in the thickness direction of the metal absorbing layer as a NiOOH film (not completely oxidized), and conversely, if the moisture from the resin film is emphasized, the barrier film is not oxidized. In the case of the nature, it is preferable to form the side of the resin film in the thickness direction of the metal absorbing layer as a NiO film (not completely oxidized).

Further, in order to have a distribution of constituent components in the thickness direction of the metal absorbing layer, it is only necessary to select four gas discharge pipes 125, 126, and 127. The reactive gas introduced at 128 may be obtained by the gas environments 161, 162, 163, and 164 in the vicinity of each gas discharge pipe. For example, when water is introduced from the gas discharge pipe 125, it is easy to form a NiOOH film on the resin film side in the thickness direction of the metal absorbing layer, and when water is introduced from the gas discharge pipe 128, it is easy to be on the resin film side in the thickness direction of the metal absorbing layer. A NiO film is formed. Further, argon as a sputtering gas and oxygen and water as a reactive gas are supplied into and discharged from the vacuum chamber.

(5) Electrode substrate film

(5-1) The electrode substrate film of the present invention can be obtained by subjecting the laminated film of the laminated thin film of the present invention to etching treatment and wiring the metal laminated wires having a line width of 20 μm or less. Specifically, the electrode substrate film shown in FIG. 4 can be obtained by etching the laminated film of the laminated thin film shown in FIG. 3 .

That is, the electrode substrate film shown in FIG. 4 includes a transparent substrate 70 including a resin film, and the metal absorbing layers 71 and 73 which are the first layer from the transparent substrate 70 side, and are provided on the transparent substrate 70. The circuit pattern of the mesh structure of the metal-made laminated thin wires on both sides, wherein the metal laminated thin wires have a line width of 20 μm or less; the second layer of metal layers 72, 75, 74, and 76; and the third layer of the second metal absorbing layer 77 78.

The electrode substrate film of the present invention can be used for a touch panel by forming an electrode (wiring) pattern of the electrode substrate film into a stripe shape or a lattice shape of the touch panel. In addition, since the metal laminated thin wires which are formed into the electrode (wiring) pattern by wiring are maintained in the laminated structure of the laminated thin film, it is extremely difficult to provide a circuit pattern such as an electrode provided on the transparent substrate even under high-intensity illumination. The identified electrode substrate film.

(5-2) Further, the electrode substrate film to be processed from the laminate film of the present invention can be processed by a known subtractive process.

In the subtractive method, a photoresist film is formed on the surface of the laminated film of the laminated film, and the portion where the wiring pattern is to be formed is exposed and developed so as to leave the photoresist film, and no light is present on the surface of the laminated film. A method of forming a wiring pattern by removing a laminated film of a portion of the resist film by chemical etching.

An aqueous solution of ferric chloride or an aqueous solution of copper chloride can be used as the etching solution for chemical etching described above.

[Examples]

Hereinafter, the examples of the present invention will be specifically described by way of comparative examples, but the present invention is not limited by the following examples.

[Examples 1 to 6]

The film forming apparatus (sputter web coater) shown in Fig. 5 was used, and oxygen was used as the reactive gas system, and the can roller 16 was made of stainless steel having a diameter of 600 mm and a width of 750 mm, and hard chromium plating was applied to the surface of the roll body. The feed roller 15 and the rear feed roller 21 are made of stainless steel having a diameter of 150 mm and a width of 750 mm, and hard chromium plating is applied to the surface of the roller body. Further, on the upstream side and the downstream side of each of the magnetron sputtering cathodes 17, 18, 19, 20, gas discharge pipes 25, 26, 27, 28, 29, 30, 31, 32 are provided, and the magnetron sputtering cathode is provided. 17, 18 are mounted with a Ni-Cu target for the metal absorbing layer, and a Cu target for the metal layer is mounted on the magnetron sputtering cathodes 19 and 20.

In addition, the magnetron sputtering cathodes 17, 18 of FIG. 5 correspond to the magnetron sputtering cathodes 117, 118 of FIG. 6, and further, the gas discharge tube of FIG. The 25, 26, 27, and 28 series correspond to the gas discharge pipes 125, 126, 127, and 128 in Fig. 6.

Further, 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 roller 16 was cooled to 0 °C. Further, the vacuum chamber 10 was evacuated to 5 Pa by a plurality of dry pumps, and further evacuated to a range of 1 × 10 ^-4 Pa using a plurality of turbomolecular pumps and a low temperature coil.

The argon gas introduced into the vacuum chamber 10 is argon gas which has not passed through the water as it is not specified, and is not argon gas which has passed through the water. After the transfer rate of the resin film was 2 m/min, 300 sccm of argon gas was introduced from the gas discharge pipes 29, 30, 31, and 32, and the cathodes 19 and 20 were controlled by electric power to obtain a Cu film thickness of 80 nm to form a film. . On the other hand, from the gas discharge pipes 25, 26, 27, 28 (gas discharge pipes 125, 126, 127, 128 in Fig. 6) shown in Fig. 5, the argon gas and the argon gas which have passed through the water are combined. A mixed gas obtained by mixing 280 sccm and 15 sccm of oxygen is introduced into the vacuum chamber 10. With respect to the cathodes 17 and 18 (the magnetron sputtering cathodes 117, 118 in Fig. 6) shown in Fig. 5, Ni- is obtained. The electric power of the Cu oxide film having a thickness of 30 nm was controlled to form a film, and the water pressure was controlled by the mixing ratio of the bubble argon gas and the argon gas. Further, the above-described water pressure is adjusted so that the (H ₂ /Ar) ratio measured by the quadrupole mass spectrometer provided in the vacuum chamber 10 is constant.

Further, it is preferable to use the above argon gas which is a sputtering gas for each carrier gas. The content of the water contained in the reactive gas may be set to a certain amount of offset in consideration of the reflectance and etching property of the metal absorbing layer formed.

Further, the partial pressures of water and hydrogen contained in the reactive gases of Examples 1 to 6 and the oxygen flow rate are shown in Tables 1 to 2 below. Further, since the deposition rate of the metal absorbing layer can be predicted by the amount of water and oxygen introduced from the gas discharge pipe, it is necessary to adjust the sputtering power in order to obtain the film thickness of the target metal absorbing layer. Further, in the film forming apparatus to which the embodiment is applied, the magnetron sputtering first cathode 117 and the magnetron sputtering second cathode 118 are not subjected to differential exhaust, and the gas environments 161, 162, and 163 shown in FIG. 164 is not independent.

Thus, a laminate film of Examples 1 to 6 comprising a transparent substrate and a laminate film comprising an elongated PET film comprising a Ni-Cu oxide film provided on the transparent substrate is obtained. A metal absorbing layer and a metal layer belonging to the Cu film.

[Comparative Example 1]

The same procedure as in Example 1 was carried out except that the reactive gas did not contain water.

In other words, except that the gas discharge tubes 125 and 126 of the first cathode 117 of the magnetron sputtering and the gas discharge tubes 127 and 128 of the second cathode 118 of the magnetron sputtering are not introduced into the water portion, In the same manner as in the first embodiment, a laminate film of Comparative Example 1 comprising a transparent substrate and a laminate film comprising an elongated PET film comprising Ni-based on the transparent substrate was produced. A metal absorbing layer of the Cu oxide film and a metal layer belonging to the Cu film.

[evaluation test]

(1) Each of the laminate thin films of Examples 1 to 6 and Comparative Example 1 (having a metal absorbing layer and a second layer including the first layer from the transparent substrate side) After the film formation of the laminated film of the copper layer was started, samples were taken at positions of 100 m and 500 m, and the spectral reflectance characteristics and etching properties of the respective laminated thin films were evaluated.

(2) Regarding the spectral reflection characteristics of the laminate film, the spectral reflection characteristics of the metal absorption layer of the first layer were evaluated by using a self-recording spectrophotometer through a transparent substrate.

(3) Regarding the etching property of the laminated film, the laminated film (metal absorbing layer and copper layer) is chemically etched using an aqueous solution of ferric chloride as an etching liquid.

The evaluation of the etching property described above was carried out by marking the merits and demerits (○, ×) in accordance with the following criteria.

"○": It is impossible to confirm the etching residue by visual observation, but it is practical.

"X": Visually observed, covering a wide range to confirm the etching residue.

(4) The evaluation results are shown in Table 1 below.

[confirm]

(1) In the laminated film of Examples 1 to 6 in which the metal absorbing layer is formed while the water is contained in the reactive gas to replenish the amount of the water in the vacuum chamber, Table 1 - Table 2 In the case of the "etching property" column, it is confirmed that the etching property of the laminated film at the end of the film formation is less than the etching property of the laminated film at the film forming start end side, and the water is not In the laminated thin film of Comparative Example 1 which is formed by forming a metal absorbing layer by a reactive gas, the above-mentioned conventional problems are not solved.

(2) Further, in Example 1 (hydrogen partial pressure: 0.022 Pa) having an oxygen flow rate of 15 sccm, Example 3 (hydrogen partial pressure: 0.066 Pa), and Example 5 (hydrogen partial pressure: 0.004 Pa), etching property The merits and demerits were not confirmed. However, it was confirmed that the higher the partial pressure of hydrogen, the reflectance showed a lower value (in the third embodiment, the partial pressure of hydrogen was 0.066 Pa, the reflectance was 21%, and the partial pressure of hydrogen was 0.022 Pa). In Example 1, the reflectance was 23%, and in Example 5 in which the hydrogen partial pressure was 0.004 Pa, the reflectance was 24%).

(3) Further, Example 2 (oxygen flow rate: 13 sccm) having a hydrogen partial pressure of 0.004 Pa, Example 4 (oxygen flow rate: 16 sccm), and Example 5 (oxygen flow rate: In the case of 15 sccm), the etchability was not confirmed. However, it was confirmed that the oxygen flow rate was high, and the reflectance showed a low value (in the fourth embodiment, the oxygen flow rate was 16 sccm, the reflectance was 22%, and the oxygen flow rate was 15 sccm. In Example 5, in Example 2 in which the reflectance was 24% and the oxygen flow rate was 13 sccm, the reflectance was 28%).

(4) A multilayer thin film formed by forming a second metal absorbing layer which is a third layer from the transparent substrate side on the copper layer is produced, and when the etching property of the second metal absorbing layer is evaluated, it is confirmed It is quite good. This is considered to be because the copper layer of the second layer is counted from the side of the transparent substrate.

[Industrial availability]

The laminate film of the present invention is excellent in etchability, and the electrode or the like of the electrode substrate film of the present invention produced by using the laminate film is difficult to be recognized even under high-intensity illumination, and therefore can be used for FPD (planar). The industrial possibilities of the "touch panel" on the surface of the display.

60‧‧‧Resin film (transparent substrate)

61‧‧‧Metal absorption layer

62‧‧‧Metal layer (copper layer) formed by dry film formation

63‧‧‧Metal absorption layer

64‧‧‧Metal layer (copper layer) formed by dry film formation

65‧‧‧Metal layer (copper layer) formed by wet film formation

66‧‧‧Metal layer (copper layer) formed by wet film formation

67‧‧‧2nd metal absorbing layer

68‧‧‧2nd metal absorbing layer

Claims (16)

A laminated body film comprising a transparent substrate including a resin film and a laminated film provided on at least one surface of the transparent substrate, wherein the laminated film has a first thickness from the transparent substrate side. a metal absorbing layer of the layer and a metal layer of the second layer, and the metal absorbing layer is formed by a reaction film forming method using a metal material and an oxygen-containing reactive gas, wherein the metal material is made of a Ni-containing monomer or It is composed of an alloy of two or more elements of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and the reactive gas contains water. The laminate film according to claim 1, wherein the metal layer has a film thickness of 50 nm or more and 5000 nm or less. The laminate film according to claim 1, wherein the laminate film has a second metal absorption layer which is calculated as a third layer from the transparent substrate side, and the second metal absorption layer is formed by using a metal material and an oxygen-containing reactive gas. The reaction is carried out by a film formation method, and the metal material is an alloy containing two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The above reactive gas contains water. The laminate film according to claim 1 or 3, wherein the alloy is made of a Ni-based alloy to which one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added. Composition. An electrode substrate film comprising: a transparent substrate including a resin film; and an electrode substrate film including a circuit pattern of a mesh structure provided on at least one surface of the transparent substrate; The metal laminated thin wire has a line width of 20 μm or less, has a metal absorbing layer of the first layer from the transparent substrate side, and a metal layer of the second layer, and the metal absorbing layer is made of a metal material and oxygen-containing reactivity. The gas is formed by a reaction film formation method, and the metal material is composed of a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy is composed of the above-mentioned reactive gas containing water. The electrode substrate film according to claim 5, wherein the metal layer has a film thickness of 50 nm or more and 5000 nm or less. The electrode substrate film according to claim 5, wherein the metal laminated thin wire has a second metal absorbing layer which is calculated as a third layer from the transparent substrate side, and the second metal absorbing layer is reacted by using a metal material and oxygen. The gas is formed by a reaction film formation method, and the metal material is composed of a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy is composed of the above-mentioned reactive gas containing water. The electrode substrate film according to claim 5 or 7, wherein the alloy is made of a Ni-based alloy to which one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added. Composition. A method for producing a laminate film comprising a transparent substrate comprising a resin film and a laminate film provided on at least one surface of the transparent substrate, characterized in that: the first step is By using a reaction film formation method using a metal material and an oxygen-containing reactive gas, formation is performed from the transparent substrate side of the above laminated film. In the metal absorbing layer of the first layer, the metal material is composed of a Ni-containing monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. In the second step, a metal layer formed as a second layer from the transparent substrate side of the laminated film is formed by a film forming method using a metal material; and the reactive gas in the first step contains water. . The method for producing a laminate film according to claim 9, further comprising a third step of forming a film formation method using a metal material and an oxygen-containing reactive gas, and forming the film from the transparent substrate side of the laminate film a second metal absorbing layer of three layers, wherein the metal material is composed of a Ni monomer or two or more elements selected from the group consisting of Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. The alloy is composed of the alloy, and the reactive gas in the third step contains water. The method for producing a laminate film according to claim 9 or 10, wherein the alloy is made of Ni added with one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu. It is composed of an alloy. The method for producing a laminate film according to claim 9 or 10, wherein the content of the water contained in the reactive gas is set to be a quantity of the amount of reduction of the residual moisture in the film forming chamber in the first step and the third step. . The method for producing a laminate film according to claim 12, wherein a ratio of a content of hydrogen molecules measured by a gas component detecting means provided in the film forming chamber to a content of an argon atom belonging to a sputtering gas (H ₂ /Ar) In a certain manner, the content of water contained in the reactive gas is set to supplement the amount of reduction in residual moisture in the film forming chambers in the first step and the third step. The method for producing a laminate film according to claim 13, wherein the gas component detecting means is configured by a quadrupole mass spectrometer, and the content of the hydrogen molecule measured by the quadrupole mass spectrometer is detected as a hydrogen ion current value, and the quadrupole mass spectrometer is used. The content of the measured argon atoms was detected as the argon ion current value. A method for producing an electrode substrate film, comprising: a transparent substrate including a resin film; and a method for producing an electrode substrate film including a circuit pattern of a mesh structure provided on at least one surface of the transparent substrate; The laminated film of the laminated thin film according to any one of claims 1 to 3 is subjected to a chemical etching treatment, and the metal laminated thin wires having a line width of 20 μm or less are subjected to wiring processing. A method for producing an electrode substrate film, comprising: a transparent substrate including a resin film; and a method for producing an electrode substrate film including a circuit pattern of a mesh structure provided on at least one surface of the transparent substrate; The laminated film of the laminated thin film of the claim 4 is subjected to a chemical etching treatment, and the metal laminated thin wires having a line width of 20 μm or less are subjected to wiring processing.