TW201922487A - Thin film metal foil with metal substrate, metal-coated transparent substrate material, laminate for see-through electrode, and see-through electrode material and device capable of effectively forming ultra-fine wiring with less transmission loss by photolithography - Google Patents

Abstract

The present invention provides a thin film metal foil with metal substrate, which can effectively form ultra-fine wiring with less transmission loss by photolithography. The thin film metal foil with metal substrate is provided with a thin film metal foil, a release layer and a metal substrate. The thin film metal foil has a first main surface and a second main surface. The release layer is disposed on the first main surface and has conductivity. The metal substrate is disposed on the release layer. The first main surface of the thin film metal foil has fine concavities and convexities each of which has a ten-point average roughness (Rz) of 2.5 [mu]m or less, and the aspect ratio (Str) of the surface property of the first main surface is 0.5 or more and 1.0 or less.

Description

Thin film metal foil with metal substrate, transparent metal substrate material, laminated plate for see-through electrode, see-through electrode material and device

The present invention relates to a film metal foil with a metal substrate, a metal-coated transparent substrate material, a laminate for a see-through electrode, a see-through electrode material, and a device.

BACKGROUND OF THE INVENTION Electronic devices in which a touch panel module is disposed in front of an image display device such as a smart phone, an input board, a car navigation device, a personal computer, a game machine, an automatic teller machine, or a television have been widely used. The image display device has an image display function capable of displaying an image in a display area. The touch panel module is used in combination with an image display device such as a liquid crystal display, and functions as an input device that senses a position where the display region of the output image is touched.

The touch panel module includes a touch panel sensor and a control unit for controlling the same. The touch panel sensor is provided with a sensing electrode for presenting a 2-dimensional coordinate composed of an X-axis and a Y-axis. The sensing electrode is composed of a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes. The touch panel sensor is configured by laminating a member for a touch panel sensor including an X electrode and a member for a touch panel sensor having a Y electrode. Hereinafter, the X electrode or the Y electrode sometimes means a see-through electrode.

In recent years, a member for a touch panel sensor has been developed, which is provided with a see-through electrode which is miniaturized (hereinafter referred to as fine patterning) and has high sensing sensitivity and can be used in combination with a high-resolution image display device. If a thick metal layer is used as the material for fabricating the finely patterned transparent electrode, the etching time to the surface of the substrate is increased, resulting in the verticality of the sidewall of the transparent electrode being broken, when the transparency is desired. When the line width of the electrode is narrow, there is also a flaw in the line. Therefore, the thickness of the metal layer for fine pattern use must be 9 μm or less.

In the case of the metal layer material for the fine pattern use, Patent Document 1 discloses a copper foil with a carrier which is sequentially provided on the surface of the electrolytic copper foil carrier having a thickness (the surface formed on the side of the electrolytic drum at the time of manufacture) The middle layer and extremely thin copper foil. The intermediate layer is configured to peel the ultra-thin copper layer from the carrier. Further, in Patent Document 1, a method for producing a copper foil with a carrier discloses a method of disposing a surface-ground electrolytic drum in an electrolytic cell and an electrode disposed around the electrolytic drum at a predetermined electrode distance, and then depositing The copper strip on the surface of the rotating electrolytic drum is peeled off, and an electrolytic copper foil carrier having a thickness of 18 μm is continuously obtained, and an intermediate layer is formed on the surface (light surface) of the electrolytic drum side of the obtained electrolytic copper foil carrier, followed by the intermediate layer. An extremely thin copper layer is formed by electroplating.

PRIOR ART DOCUMENT Patent Document Patent Document 1: Japanese Patent Laid-Open No. 2017-88961

SUMMARY OF THE INVENTION However, when an ultra-thin copper foil having a line width of less than 5 μm is formed by photolithography using an ultra-thin copper foil as described in Patent Document 1, the wiring has a problem of disconnection. In general, when the alternating current is distributed to the wiring, the current concentrates on the wiring surface due to the skin effect. Therefore, when the ultra-thin copper foil as described in Patent Document 1 is used, the height difference is large. When the wiring of the copper foil having a long cross-section has a high-frequency alternating current, the transmission loss is increased.

Here, the height difference is as shown in FIG. 13, which means that when the copper foil sample 100 is cut in a vertical plane, the maximum top height Hp of the unevenness of the section curve 101 of the slit relative to the average height L3 of the convex portion appears. The sum of the maximum bottom depth Hv (height difference = Hp + Hv). As shown in FIG. 13, the length of the section is the length of the section curve 101, and the ratio of the length L1 of the section curve 101 to the length L2 of the reference line 102 is also expressed as one of the indexes indicating the above-described height difference.

Accordingly, an object of the present invention is to provide a thin film metal foil with a metal substrate which can effectively form ultrafine wiring with low transmission loss by photolithography, a transparent metal substrate material, a laminate for a see-through electrode, Such manufacturing methods, see-through electrode materials and devices.

A film metal foil with a metal substrate according to a first aspect of the invention, comprising: a film metal foil having a first main surface and a second main surface; a peeling layer provided on the first main surface and having conductivity; and a metal a base material provided on the release layer; the first main surface of the thin film metal foil has fine concavities and convexities having a ten-point average roughness (Rz) of 2.5 μm or less, and an aspect ratio of a surface property of the first main surface (Str) is 0.5 or more and 1.0 or less.

The metal-coated transparent substrate material of the second invention comprises: a transparent substrate; the metal foil with the metal substrate described above, which is provided on one or both sides of the transparent substrate; and a transparent adhesive layer which is located in the transparent Between the substrate and the aforementioned thin film metal foil.

In the laminated electrode for a see-through electrode according to a third aspect of the invention, the metal base material and the release layer are formed by peeling off the metal-coated transparent base material.

The see-through electrode material according to the fourth aspect of the invention includes a wiring pattern layer in which the film metal foil of the multilayer electrode laminate has an opening.

A device according to a fifth aspect of the invention includes the above-described see-through electrode material and a control circuit that is electrically connected to the wiring pattern layer.

A see-through electrode material according to a sixth aspect of the invention includes: a transparent substrate; and a wiring pattern layer formed on one surface or both surfaces of the transparent substrate and having a thickness of 0.1 μm or more and 5.0 μm or less; and the wiring pattern layer is transparent The thin film metal foil bonded to the transparent substrate is formed by patterning, and the ten-point average roughness (Rz) of the surface of the wiring pattern layer is 2.5 μm or less, and the aforementioned wiring pattern layer is formed. The aspect ratio (Str) of the surface property of the surface is 0.5 or more and 1.0 or less.

Advantageous Effects of Invention According to the present invention, ultrafine wiring having a small transmission loss can be efficiently formed by photolithography.

Embodiments for Carrying Out the Invention Hereinafter, embodiments of the present invention will be described. In the same manner, the same components will be denoted by the same reference numerals and will not be described.
(1) Film metal foil with metal substrate

As shown in FIG. 1A, the metal foil 10 with a metal substrate of the present embodiment includes a thin film metal foil 11, a peeling layer 12, a metal base material 13, and a laminated plate for lowering the reflective layer 14. The thin film metal foil 11 has a first main surface T11 and a second main surface B11. The peeling layer 12 and the metal base material 13 are sequentially disposed on the first main surface T11. The lower reflection layer 14 is provided on the second main surface B11.

In the present embodiment, the aspect ratio (Str) of the surface property of the first main surface T11 of the thin film metal foil 11 is 0.5 or more and 1.0 or less, and the tenth point average roughness of the first main surface T11 of the thin film metal foil 11 is obtained. (Rz) is 2.5 μm or less. Here, the three-dimensional surface property parameter which quantifies the intensity of the isotropic or anisotropy of the surface defined by Str ISO 25178 is a value of 0 or more and 1 or less. When Str is near 1, its surface will show obvious isotropy. When Str is near 0, its surface will show obvious anisotropy. Here, isotropic means that the surface unevenness does not have a regular directionality, that is, no texture or the like on the surface. Anisotropy means that the surface irregularities are visible in the directionality, that is, the texture on the surface. Rz means the ten point average roughness specified in JIS B0601 (1994).

In other words, in the present embodiment, the first main surface T11 of the thin film metal foil 11 is a smooth surface (hereinafter referred to as a high smooth surface) having a convex portion (mountain) or a concave portion (valley) which is less likely to protrude. The wiring using the thin film metal foil 11 has a smaller transmission loss than the wiring using the conventional ultra-thin copper foil, and the effect is particularly remarkable when the frequency of the alternating current flowing to the wiring is high. It is presumed that the cross-sectional length of the first main surface T11 of the wiring using the thin film metal foil 11 is shorter than that of the conventional ultra-thin copper foil, and therefore the alternating current flows due to the alternating current flowing along the surface shape of the wiring due to the skin effect. The distance is shorter than ever, so the transmission loss of the signal will become smaller. Further, even when wiring is formed on the thin film metal foil 11 having the first main surface T11 having high smoothness by photolithography, the occurrence of disconnection can be suppressed more than in the past, so that ultrafine wiring can be efficiently formed. It is presumed that the main factor is as follows: when a photoresist film is formed on the first main surface T11 of the thin film metal foil 11 and exposed to form a predetermined wiring pattern, the penetration is performed as compared with the case of using a conventional ultra-thin copper foil. The exposure of the photoresist layer is not easily diffused and reflected on the first main surface T11, so that a photoresist layer having a desired opening shape can be formed; and when the thin film metal foil 11 is subjected to photolithography, the etching liquid is less likely to occur along the surface of the copper foil. Since the directional unevenness is diffused, the etching reaction easily proceeds in the thickness direction of the thin film metal foil 11. Here, the wiring having an ultrafine wiring line width of less than 10 μm is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 4.0 μm or less, and more preferably 1.0 μm or more and 3.0 μm or less. In the present embodiment, the surface property of the first main surface T11 of the thin film metal foil 11 is defined by Str in order to more accurately grasp whether or not the transmission loss is higher than the conventional Rz and the arithmetic mean roughness ( Ra) or the like is less as an evaluation index of surface properties; and whether or not ultrafine wiring can be efficiently formed by photolithography. Here, Ra means the arithmetic mean roughness specified in JIS B0601 (1994).

In the present embodiment, the film metal foil 10 with a metal base material is provided with the reflection-reducing layer 14, but the present invention is not limited thereto, and the film metal foil 10 to which the metal substrate is attached may not have the reflection-reducing layer 14.
(1.1) Thin film metal foil

The thin film metal foil 11 is suitable for use as an electrode material such as a touch panel sensor, an electromagnetic wave absorbing plate, an in-vehicle antenna, or a printed wiring board.

The Str of the first main surface T11 of the thin film metal foil 11 is 0.5 or more and 1.0 or less, and preferably 0.55 or more and 1.0 or less, and more preferably 0.6 or more and 1.0 or less. The Rz of the first main surface T11 of the thin film metal foil 11 is 2.5 μm or less, preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.01 μm or more and 1.8 μm or less. When the ultrafine wiring is formed by using the thin film metal foil 11 in which the Str of the first main surface T11 of the thin film metal foil 11 is less than 0.5 and the Rz exceeds 2.5 μm, the ultrafine wiring is easily broken and the ultrafine layer is formed. The transmission loss of wiring is greatly increased.

The thickness of the thin film metal foil 11 is preferably 0.1 μm or more and 5.0 μm or less, and more preferably 0.5 μm or more and 3.0 μm or less. When the thickness of the thin film metal foil 11 is within the above range, it is easier to form ultrafine wiring by photolithography.

The first main surface T11 of the thin film metal foil 11 has a high smooth surface as described above, but still has fine irregularities having an Rz of 2.5 μm or less. The height difference of the fine unevenness is preferably 2.3 μm or less, more preferably 1.9 μm or less, and still more preferably 1.7 μm or less. The cross-sectional length of the first main surface T11 of the film metal 11 is preferably 1.10 times or less with respect to the length of the reference line. The ultrafine wiring formed using the thin film metal foil 11 has an advantage of reducing transmission loss particularly when a high frequency alternating current flows.

The material constituting the thin film metal foil 11 preferably contains, for example, at least one selected from the group consisting of copper, nickel, aluminum, and silver. In particular, the material of the film metal foil 11 is preferably composed of copper as a main component, and the film metal foil 11 preferably contains 80% by mass or more of copper based on the total mass of the film metal foil 11, and more preferably contains 85% by mass or more. It should preferably contain 90% by mass or more. The size of the film metal foil 11 may be appropriately adjusted depending on the use of the film metal foil 10 to which the metal substrate is attached.

In the present embodiment, the peeling layer 12 is directly formed on the first main surface T11 of the thin film metal foil 11, and the reflection reducing layer 14 is directly formed on the second main surface B11, but, for example, may also be in the first main A rust-preventing treatment layer, a decane coupling treatment layer, and the like are formed between the surface T11 and the peeling layer 12 and between the second main surface B11 and the reflection-reducing layer 14. When the rust-preventing treatment layer is formed, the film metal foil 11 can be prevented from being discolored (corroded). When the decane coupling treatment layer is formed, the adhesion strength between the thin film metal foil and the transparent adhesive layer can be improved in the metal-coated transparent base material 20 described later. As the material constituting the rust-preventing treatment layer, for example, a zinc plating material, a zinc alloy plating material, a tin plating material, a tin alloy plating material, a nickel plating material, a chromate or the like can be used. The thickness of the rust-preventing treatment layer is preferably 0.001 μm or more and 0.50 μm or less. The decane coupling agent constituting the decane coupling treatment layer may be, for example, 3-(2-aminoethyl)aminopropyltrimethoxy decane, 3-glycidoxypropyltrimethoxy decane or 3-aminopropyltriethoxy decane. , 3-mercaptopropyltrimethoxydecane or 3-phenylaminopropyltrimethoxydecane. The thickness of the decane coupling treatment layer is preferably 0.001 μm or more and 0.50 μm or less.
(1.2) peeling layer

The release layer 12 mainly has an effect of easily peeling the metal substrate 13 from the film metal foil 10 to which the metal substrate is attached. The peeling layer 12 has a first major surface T12 and a second major surface B12, and covers the entire surface of the first major surface T11 of the thin film metal foil 11. Str of the first main surface T12 and the second main surface B12 of the peeling layer 12 is 0.5 or more and 1.0 or less, preferably 0.55 or more and 1.0 or less, and more preferably 0.6 or more and 1.0 or less. The Rz of the first main surface T12 and the second main surface B12 of the peeling layer 12 is 2.5 μm or less, preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.01 μm or more and 1.8 μm or less. The thickness of the metal constituting the peeling layer 12 is preferably 0.001 μm or more and 0.50 μm or less. When the thickness of the peeling layer 12 is within the above range, the surface properties of the first main surface T12 and the second main surface B12 of the peeling layer 12 follow the surface property of the second main surface B13 of the metal base material 13, and thus the peeling layer 12 is removed. The surface properties of the first main surface T12 and the second main surface B12 and the surface properties of the second main surface B13 of the metal base material 13 can be evaluated to be the same. The thickness of the peeling layer 12 can be calculated by a gravimetric method. The material constituting the peeling layer 12 may be an alloy or an oxide composed of a single or a plurality of kinds of nickel, molybdenum, chromium, iron, titanium, tungsten, or phosphorus. Thereby, the peeling layer 12 has conductivity, and the thin film metal foil 11 can be formed on the peeling layer 12 by electroplating. It is preferable that the first main surface T12 side of the peeling layer 12 is mainly composed of an alloy and the second main surface B12 side is mainly composed of an oxide layer. Thereby, the metal substrate 13 can be peeled off from the film metal foil 10 attached to the metal substrate together with the peeling layer 12, and the peeling layer 12 can be peeled off from the film metal foil 11.
(1.3) Metal substrate

The metal base material 13 has a small thickness and can function as a reinforcing material (carrier) of the film metal foil 11 having low mechanical strength. The metal base material 13 has a first main surface T13 and a second main surface B13, and covers the entire surface of the first main surface T12 of the peeling layer 12. The thickness of the metal base material 13 is not particularly limited as long as it has a mechanical strength capable of functioning as a carrier of the thin film metal foil 11, and is preferably 7 μm or more and 40 μm or less, more preferably 7 μm or more and 36 μm or less, and more preferably 10 μm. Above and below 20 μm. The thickness of the metal substrate 13 can be calculated by a gravimetric method.

The material constituting the metal base material 13 preferably contains, for example, one selected from the group consisting of copper, nickel, aluminum, magnesium, tungsten, molybdenum, platinum, gold, and palladium (hereinafter referred to as component A). In addition, the content of the component A is preferably 80% by mass or more, and more preferably 85% by mass or more, and more preferably 90% by mass or more based on the total mass of the metal base material 13. Based on the cost perspective, copper should be used. As the metal base material 13 for copper, for example, an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil, a rolled copper alloy foil, or the like can be used. The surface property of the first main surface T11 of the thin film metal foil 11 is subjected to the surface property of the second main surface B13 of the metal base material 13 via the peeling layer 12, as shown in the method for producing a thin metal foil with a metal substrate, which will be described later. Since the influence on the second main surface B13 of the metal base material 13 is 0.5 or more and 1.0 or less, and preferably 0.55 or more and 1.0 or less, it is preferably 0.6 or more and 1.0 or less. The Rz of the second main surface B13 of the metal base material 13 is 2.5 μm or less, and preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.01 μm or more and 1.8 μm or less.
(1.4) Lowering the reflective layer

The reflection-reducing layer 14 is a material of the first reflection-reducing pattern layer 41A and the second reflection-reducing pattern layer 41B (hereinafter sometimes referred to as a reflection-reducing pattern layer 41A, 41B) in the see-through electrode material 40 shown in FIG. 2B.

The lower reflection layer 14 has a first main surface T14 and a second main surface B14. The lower reflection layer 14 covers the entire surface of the second main surface B14 of the transparent adhesive layer 22A in the embodiment shown in FIG. 2A, and in the embodiment shown in FIG. 2B, the lower reflection layer 14 corresponds to the lower reflection pattern layer 41, which is not covered. The second main surface B14 of the transparent adhesive layer 22A is entirely flat. The thickness of the reflection-reducing layer 14 is preferably 0.001 μm or more and 0.50 μm or less, and more preferably 0.01 μm or more and 0.30 μm or less. When the thickness of the reflective layer 14 is lowered within the above range, reducing the surface properties of the first main surface T14 and the second main surface B14 of the reflective layer 14 follows the surface property of the second main surface B11 of the thin film metal foil 11, thereby The surface of the first main surface T14 and the second main surface B14 of the reflection reducing layer 14 is formed to have a surface property similar to that of the second main surface B11 of the thin film metal foil 11 . Reducing the thickness of the reflective layer 14 can be calculated by the gravimetric method.

The material constituting the reflection-reducing layer 14 may be a metal such as copper, nickel, cobalt, tungsten or aluminum, or the like, and may further contain sulfur or the like. The material constituting the reflection-reducing layer 14 is a metal, and in the see-through electrode material 40 shown in FIG. 2B, the first wiring pattern layer 42A and the second wiring pattern layer 42B can be lowered (hereinafter sometimes referred to as a wiring pattern layer). Wiring resistance of 42A, 42B). In particular, the reflection-reducing layer 14 preferably contains at least one selected from the group consisting of sulfur, nickel, cobalt, tungsten, and aluminum at a content ratio of 0.1% or more and 10.0% or less per unit area. Thereby, the high reflectance of the surface characteristics of the thin film metal foil 11 at a wavelength of 550 nm or more and 780 nm or less can be suppressed, and the average reflectance can be obtained in the range of 380 nm or more and 780 nm or less. Therefore, in the see-through electrode material 40, the flash of the surface of the wiring pattern layers 42A and 42B can be suppressed, and when the see-through electrode material 40 is used for a liquid crystal display or the like, the contrast of the screen can be suppressed from being small. At this time, the sulfur content is preferably within 10%. When the sulfur content is within the above range, the resistance values of the wiring pattern layers 42A and 42B themselves are not easily increased. In addition, the content per unit area is analyzed by a commercially available energy dispersive X-ray spectroscope (EDS) or a commercially available wavelength dispersive X-ray spectroscope (WDS) attached analysis device (using a computer drawing result) The value obtained (% by weight).

The light reflectance of the reflection-reducing layer 14 in the visible light region (380 nm or more and 780 nm or less) is preferably 20% or less, more preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less. The light reflectance in the visible light region is a value measured by a method in accordance with "JIS K 7375 Plastic - Total Light Transmittance and Total Light Reflectance".
(2) Metal-coated transparent substrate material

As shown in FIG. 1B, the metal-coated transparent substrate material 20 of the present embodiment includes a transparent substrate 21, a first transparent adhesive layer 22A, a first metal-clad metal foil 10A, and a second transparent adhesive layer 22B. The second film metal foil 10B with a metal substrate. The transparent substrate 21 has a first main surface T21 and a second main surface B21. The first transparent adhesive layer 22A and the first metal foil-attached metal foil 10A are sequentially laminated on the first main surface T21 of the transparent substrate 21. The second transparent adhesive layer 22B and the second metal foil-attached metal foil 10B are sequentially laminated on the second main surface B21 of the transparent substrate 21. The film metal foil 10A of the first metal substrate and the film metal foil 10B of the second metal substrate and the film metal foil 10 with the metal substrate have the same configuration. Hereinafter, the first transparent adhesive layer 22A and the second transparent adhesive layer 22B may be referred to as transparent adhesive layers 22A and 22B. In the present embodiment, the metal-coated transparent substrate material 20 includes the first metal-attached metal foil 10A and the second metal-coated thin-film metal foil 10B, but the invention is not limited thereto, and the metal is covered. The transparent substrate material 20 may also have only the film metal foil 10A of the first metal-attached substrate.
(2.1) Transparent substrate

The transparent substrate 21 has a plate shape. The thickness of the transparent substrate 21 may be appropriately selected depending on the use of the metal-coated transparent substrate material 20, and is preferably 24 μm or more and 300 μm or less, and more preferably 35 μm or more and 260 μm or less. When the thickness of the transparent substrate 21 is within the above range, wrinkles are less likely to occur, and it is easy to handle and has good transparency. The material constituting the transparent substrate 21 may be, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) or polymethyl methacrylate (PMMA). Transparent resin. The transparent substrate 21 may contain an additive type or reactive flame retardant such as tetrabromobisphenol A.

Moreover, as a material other than the above, a transparent resin containing a cycloolefin may be used, or a transparent resin containing a polyester which can be strongly stretched when formed into a film to improve crystallinity and increase birefringence can be used. In particular, a see-through electrode material obtained by using a metal-coated transparent substrate material having a transparent substrate having a retardation value of, for example, a cycloolefin film of 100 nm or less, or a polyester having a retardation value of, for example, 3000 nm or more is used. The see-through electrode material obtained by the metal-coated transparent substrate material of the transparent substrate of the film has the advantages of reducing the phenomenon of rainbow spots or blackout, as will be described later.
(2.2) Transparent adhesive layer

The first transparent adhesive layer 22A fixes the thin metal foil 10A of the first metal-attached substrate on the first main surface T21 of the transparent substrate 21. The second transparent adhesive layer 22B fixes the film metal foil 10B of the second metal substrate to the second main surface B21 of the transparent substrate 21. The first transparent adhesive layer 22A and the second transparent adhesive layer 22B may have the same configuration or may be mutually different.

The transparent adhesive layers 22A, 22B are cured of a transparent adhesive. The material constituting the transparent adhesive preferably contains, for example, an acrylic resin, an epoxy resin, an urethane resin, or a mixed resin thereof. In particular, acrylic resins, urethane resins, or such mixed resins have excellent transparency and are also optically useful.

A transparent adhesive layer 22A, 22B should be of a hardness of 1.0N / mm ² or more and 200N / mm ² or less, more appropriate to 4.0N / mm ² or more and 175N / mm ² or less. When the hardness of the transparent adhesive layers 22A and 22B is within the above range, the elongation of the adhesive which is one of the causes of the disconnection can be suppressed. Here, the hardness of the transparent adhesive layers 22A and 22B is a value measured by a nanoindentation device. The thickness of the transparent adhesive layers 22A and 22B is preferably 0.5 μm or more and 10.00 μm or less, and more preferably 1.0 μm or more and 8.00 μm or less.
(3) laminated plate for see-through electrode

The laminated electrode laminate board 30 of the present embodiment is obtained by peeling the first metal base material 13A, the first peeling layer 12A, the second metal base material 13B, and the second peeling layer 12B from the metal-coated transparent base material 20. That is, as shown in FIG. 2A, the transparent electrode substrate 30 includes a transparent substrate 21, a first transparent adhesive layer 22A, a first reduced reflection layer 14A, a first thin film metal foil 11A, and a second transparent adhesive layer 22B. Second, the reflective layer 14B and the second thin film metal foil 11B are lowered. The first transparent adhesive layer 22A, the first light-reducing reflective layer 14A, and the first thin film metal foil 11A are sequentially laminated on the first main surface T21 of the transparent substrate 21. The second transparent adhesive layer 22B, the second reduced reflection layer 14B, and the second thin film metal foil 11B are sequentially laminated on the second main surface B21 of the transparent substrate 21.
(4) see-through electrode material

The see-through electrode material 40 of the present embodiment includes a first wiring pattern layer 42A, and the first thin film metal foil 11A of the laminated electrode laminated board 30 has a first opening portion A40A and a second wiring pattern layer 42B. The second thin film metal foil 11B has the second opening portion A40B. That is, as shown in FIG. 2B, the see-through electrode material 40 includes a transparent substrate 21, a first transparent adhesive layer 22A, a first reduced reflection pattern layer 41A, a first wiring pattern layer 42A, a second transparent adhesive layer 22B, and a second. The reflective pattern layer 41B and the second wiring pattern layer 42B are lowered. The first transparent adhesive layer 22A, the first reduced reflection pattern layer 41A, and the first wiring pattern layer 42A are sequentially laminated on the first main surface T21 of the transparent substrate 21. The second transparent adhesive layer 22B, the second reduced reflection pattern layer 41B, and the second wiring pattern layer 42B are sequentially laminated on the second main surface B21 of the transparent substrate 21.

The reduced reflection pattern layer 41A provided in the see-through electrode material 40 can greatly reduce the light incident from the second outer surface portion A22B (hereinafter sometimes referred to as A22B) through the transparent adhesive layer and the transparent substrate in the first wiring pattern layer. The case of scattering near the second main surface B42 of 42A. Similarly, in the lowering of the reflection pattern layer 41B, the light incident from the first outer surface portion A22A (hereinafter sometimes referred to as A22A) is scattered near the second main surface B42 of the second wiring pattern layer 42B.

The sheet resistance of the see-through electrode material 40 is preferably 0.01 Ω/sq. or more and 50 Ω/sq. or less, more preferably 0.05 Ω/sq. or more and 10 Ω/sq. or less, more preferably 0.1 Ω/sq. or more and 5 Ω. /sq. Below.

The total light transmittance of the see-through electrode material 40 is preferably 60% or more, more preferably 65% or more, and more preferably 70% or more. As long as the total light transmittance of the see-through electrode material 40 is within the above range, the see-through electrode material 40 is suitably used for a touch panel sensor or the like.
(4.1) Wiring pattern layer

After the first wiring pattern layer 42A removes one portion of the first thin film metal foil 11A by photolithography, a circuit that becomes a gap between the first openings A40A is formed in one portion of the first thin film metal foil 11A. Similarly to the first wiring pattern layer 42A, the second wiring pattern layer 42B is formed with a circuit that forms a gap between the second openings A40B in one portion of the second thin film metal foil 11B. The pattern shape of the wiring pattern layers 42A and 42B may be appropriately adjusted depending on the use of the see-through electrode material 40, and the like, and may be a mesh (lattice) shape, a parallel thin line pattern shape, a comb shape or the like. Further, in the embodiment shown in FIG. 2B, the first opening portion A40A is a portion where the portion of the first reflection-reducing layer 14A has been removed, and the second opening portion A40B is a portion where the portion of the second reflection-reducing layer 14B has been removed.

The line width W of the wiring pattern layers 42A and 42B may be appropriately adjusted in accordance with the use of the see-through electrode material 40. When the see-through electrode material 40 is used for a member for a touch panel sensor, the line width W is preferably 0.5 μm or more and 10 μm or less, and more preferably 1.0 μm or more and 8.0 μm or less. When the line width W is within the above range, the first opening portion A40A and the second opening portion A40B can be made wider and larger, and the transmittance of the see-through electrode material 40 can be further improved. The opening width W1 of the first opening A40A and the second opening A40B is preferably 50 μm or more and 10000 μm or less, and more preferably 200 μm or more and 5000 μm or less. Further, the aperture ratio is preferably 69.44% or more and less than 100% in the region where visible light is transparent, and is preferably 92.45% or more and 99.96% or less. Further, the aperture ratio is an ratio of an opening in a certain region of a surface on which a wiring pattern can be formed on a substrate, in other words, an area ratio which is not blocked by the wiring pattern.

The Str of the outer surface portions A22A and A22B is preferably 0.5 or more and 1.0 or less, more preferably 0.55 or more and 1.0 or less, and more preferably 0.6 or more and 1.0 or less. The Rz of the outer surface portions A22A and A22B is preferably 2.5 μm or less, more preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.01 μm or more and 1.8 μm or less. When the Str and Rz of the outer surface portions A22A and A22B are within the above range, the turbidity (haze) of the transparent adhesive layers 22A and 22B of the outer surface portions A22A and A22B can be 20% or less, and the see-through electrode material 40 can have More excellent perspective. Turbidity (haze) is a value that can be measured by a haze meter.
(5) device

The device 50 of the present embodiment is a mutual capacitive touch panel sensor which is one of projection type capacitive methods. As shown in FIG. 2C, the device 50 includes a see-through electrode material 40, a control wiring 51, and a cover 52. The control circuit 51 is electrically connected to the wiring pattern layers 42A and 42B. The cover 52 is attached to the surface of the see-through electrode material 40 on the side of the first wiring pattern layer 42A. In addition, the transparent adhesive layers 22A and 22B and the reduced reflection pattern layers 41A and 41B are omitted in FIG. 2C.

As shown in FIG. 2C, the device 50 is disposed on the front side of the display surface T53 of the image display device 53 so that the surface of the second electrode pattern layer 42B side of the see-through electrode material 40 is on the side of the image display device 53. The image display device 53 can use, for example, a liquid crystal display panel, a plasma image display panel, an electroluminescence (Electro Luminescence) panel, an e-book, or a Braun tube.

In the device 50, the first wiring pattern layer 42A functions as a receiving electrode, and the second wiring pattern layer 42B functions as a transmission electrode. That is, when the device is close to the surface of the cover 52, the capacitance of the capacitor formed at the intersection of the receiving electrode and the transmitting electrode changes, and the control circuit 51 detects the change of the electrostatic capacitance to specify the proximity. The location of the indicator. The indicator may be an electric conductor such as a fingertip of a user, a stylus or a pointer.

Further, when the video display device 53 shown in FIG. 2C is a liquid crystal display panel, when the screen is viewed through the polarized sunglasses, when the transparent substrate 21 used in the device 50 is made of, for example, general PET, it may be confirmed. Rainbow spot; however, if the transparent substrate 21 is made of a material having a lower retardation value than a general PET (hereinafter referred to as a low retardation material) or a material having a higher retardation value (hereinafter referred to as a high retardation material), it is reduced. The advantages of the above rainbow spots. Further, not limited to the liquid crystal display, in the case of using a polarizing plate display and viewing the screen through the polarizing sunglasses, when the transparent substrate 21 used in the device 50 is a general PET, black vision occurs (the picture is changed according to the viewing angle) Black, but not visible, and high-latency materials have the advantage of reducing blackout. Further, the low-latency material is a material having a retardation value of, for example, 100 nm or less, and examples thereof include a cycloolefin film (represented by JSR, product name ARTON; manufactured by Japan ZEON, product name ZF-140 or ZF-160). Further, the high retardation material is a material having a retardation value of, for example, 3,000 nm or more, and may be a polyester film (representing a super birefringent polyester film manufactured by Toyobo Co., Ltd., product name: SRF).

In this embodiment, the sensing mode of the device 50 is a mutual capacitance type, but the invention is not limited thereto, and may be a self-capacitance sensing method, or a self-capacitance type and a mutual capacitance type sensing method. .
(6) Method for producing a film metal foil with a metal substrate

The method for producing the metal foil 10 with a metal substrate according to the present embodiment is a film metal with a metal substrate after undergoing each step in the order of the first step, the second step, the third step, and the blackening step. Foil 10. In the present embodiment, the blackening step is included, but the present invention is not limited thereto, and the method for producing the thin film metal foil 10 with a metal substrate may not include the blackening step.
(6.1) First step

As shown in FIG. 4A, after the electrolytic drum 110 is wetted into the first electrolytic solution 121 in the first step, the obtained metal substrate 13 is peeled off from the electrolytic drum 110. Thereby, the metal base material 13 shown in FIGS. 3A and 4B can be obtained.

Specifically, as shown in FIG. 4A, the electrolytic drum 110 is used as a cathode, and a frame (not shown) having an arcuate cross section facing the electrolytic drum 110 is used as an anode, and the electrolytic drum 110 is immersed in the electrolytic solution tank 120. In the first electrolyte 121. Next, the electrolytic drum 110 is rotated to cause an electric current to flow between the anode and the cathode, whereby the metal substrate 13 is electrodeposited on the surface of the electrolytic drum 110. Further, the obtained metal base material 13 is peeled off from the electrolytic drum 110, whereby the metal base material 13 can be continuously produced. At this time, the surface of the metal base material 13 that is in contact with the electrolytic drum 110 is the first main surface T13, and the surface of the metal base material 13 that is not in contact with the electrolytic drum 110 is the second main surface B13.

The surface of the electrolytic drum 110 is ground. That is, the surface of the electrolytic drum 110 is formed with streaky uneven portions (polishing marks). Thereby, the metal substrate 13 which has been electrodeposited on the surface of the electrolytic drum 110 can be easily peeled off from the electrolytic drum 110. The material constituting the electrolytic drum 110 can be, for example, titanium or stainless steel. The size of the electrolytic drum 110 or the like may be appropriately adjusted depending on the use of the thin film metal foil 10 to which the metal substrate is attached.

The composition of the first electrolyte solution 121 may be appropriately adjusted depending on the material of the metal base material 13 or the like. When the material of the metal base material 13 is copper, the first electrolyte solution 121 preferably contains a copper compound, an acid, and a halogen monomer, and further contains a water-soluble solution. The polymer is preferred. The above-mentioned copper compound may, for example, be an inorganic salt of copper such as copper sulfate, copper nitrate or copper chloride; an organic salt of copper such as copper acetate, copper oxalate, copper alkoxide or copper acetonitrile; and the like . The above acids may, for example, be inorganic acids such as sulfuric acid, nitric acid or hydrochloric acid, and organic acids such as acetic acid, oxalic acid and dodecylbenzenesulfonic acid. The halogen monomer may be a monomer of fluorine, chlorine, bromine or iodine, and the properties (solid, liquid, gas) when the halogen monomer is used are not particularly limited. These copper compounds, acids, and halogen monomers may be contained in the first electrolyte solution 121 by selecting one or more types.

The first electrolyte solution 121 contains a water-soluble polymer, whereby the second main surface B13 of the metal base material 13 can be made into a highly smooth surface. In other words, the Str of the second main surface B13 of the metal base material 13 can be 0.5 or more and 1.0 or less, and the Rz of the second main surface B13 can be made 2.5 μm or less. As a result, the first main surface T11 of the thin film metal foil 11 can be easily made into a highly smooth surface as will be described later. The reason why the first electrolyte solution 121 contains a water-soluble polymer and the second main surface B13 of the metal base material 13 is a highly smooth surface is that the first electrolyte solution 121 can be restricted by the presence of the water-soluble polymer. The movement of copper ions in the middle. Specifically, in the electrolysis method, the current is easily concentrated to the tip end portion of the convex portion of the surface uneven portion of the electrolytic drum 110. Therefore, when the first electrolyte solution 121 does not contain the water-soluble polymer, the copper ions in the first electrolyte solution 121 are easily moved. To the surface convex portion of the electrolytic drum 110. Therefore, the metal is concentrated on the convex portion, so that the surface property of the surface (matt surface) of the side of the obtained metal substrate which is not in contact with the electrolytic drum 110 becomes larger than the side of the side opposite to the electrolytic drum 110 (glossy surface) ) is thicker. In contrast, when the first electrolyte solution 121 contains a water-soluble polymer, the copper ions are less likely to move to the surface convex portion of the electrolytic drum 110, so that the metal is easier to be used than when the first electrolyte solution 121 does not contain a water-soluble polymer. The concave portion is precipitated. It is assumed that the second main surface B13 of the metal substrate 13 is a high smooth surface. The water-soluble polymer may, for example, be a polyethylene glycol having an average molecular weight (weight average) of 500 or more and 5,000,000 or less, or a water-soluble cellulose such as gelatin, hydroxymethylcellulose or hydroxypropylcellulose having an average molecular weight of 5,000 or less and Acacia and so on.

Further, the first electrolytic solution 121 may further contain an additive such as 3-mercapto-1-propanesulfonic acid. By including the additive in the first electrolytic solution 121, the second main surface B13 which is smoother and has excellent luster and no abnormal protrusions can be obtained.

The first electrolyte solution 121 preferably contains the above-mentioned copper compound of 100 g/L or more and 300 g/L or less, the above-mentioned acid of 50 g/L or more and 150 g/L or less, and the halogen monomer of 1 mass ppm or more and 20 mass ppm or less. Further, the electrolyte solution 121 preferably contains a water-soluble polymer of 15 ppm or more and 50 ppm or less.

When the first electrolytic solution 121 contains an additive, it is preferable to contain the above-mentioned additive of 1 ppm or more and 50 ppm or less.

The production conditions of the metal base material 13 may be appropriately adjusted depending on the material of the metal base material 13 or the like. For example, the current density is preferably 1.0 A/dm ² or more and 10.0 A/dm ² or less, and the temperature of the first electrolytic solution 121 is preferably 10° C. or higher and 80° C. or lower, and the pH is preferably 5.0 or more and 9.0 or less.

The method of adjusting Str and Rz of the second main surface B13 of the metal base material 13 may be, for example, a method of adjusting the molecular weight and/or the amount of addition of the water-soluble polymer to be added. The method of adjusting the thickness of the metal base material 13 may be, for example, a method of adjusting the current density and/or immersing the drum 110 in the first electrolyte solution 121 and flowing a current.

In the surface property of the metal base material 13 obtained in the above manner, the first main surface T13 becomes thicker than the second main surface B13. It is presumed that this result is mainly due to the following factors: since the first electrolyte 121 contains a water-soluble polymer, the second main surface B13 of the metal substrate 13 becomes a smooth surface; since the metal substrate 13 is directly electrodeposited in electrolysis The surface of the drum 110 is such that the first main surface T13 of the metal base material 13 is transferred to the surface of the electrolytic drum 110 on which the polishing marks are formed.
(6.2) Second step

In the second step, the peeling layer 12 is formed on the second main surface B13 of the metal substrate 13. Thereby, the first laminate 15 shown in Figs. 3B and 4C can be obtained.

Since the peeling layer 12 is directly formed on the second main surface B13 of the metal base material 13, the surface property of the second main surface B13 of the metal base material 13 is transferred to the first main surface T12 of the peeling layer 12. Further, since the thickness of the peeling layer 12 is very thin (0.001 μm or more and 0.50 μm or less), Str and Rz of the first main surface T12 of the peeling layer 12 and Str and Rz of the second main surface B12 and the metal base material 13 can be formed. The second main surface B13 has the same peeling layer 12 as Str and Rz.

The method of forming the peeling layer 12 may be, for example, a plating method. The composition of the electrolyte used in the electroplating method may be appropriately adjusted depending on the material of the peeling layer 12, and preferably contains a metal salt, a metal oxygen compound, and an organic acid. The metal salt may be a sulfate of nickel, molybdenum, chromium, iron, titanium, tungsten, phosphorus or the like or an inorganic salt such as a nitrate or a chloride; or an acetate or an oxalate, an alkoxide or an acetonide An organic salt such as a salt; and a hydrate thereof. The metal oxide compound may be a metal acid salt such as sodium molybdate or sodium tungstate. The organic acid may be acetic acid, oxalic acid, citric acid or the like. The metal salt, the metal oxygen compound, and the organic acid may be one or more selected from the electrolyte solution forming the release layer 12, respectively.

The electrolytic solution forming the peeling layer 12 preferably contains the above metal salt of 0.6 g/L or more and 60 g/L or less (in terms of metal), 0.1 g/L or more and 10 g/L or less (in terms of metal) of the above metal oxide compound, 0.1 The above organic acid having a g/L or more and 300 g/L or less.

The manufacturing conditions of the plating method may be appropriately adjusted depending on the material of the peeling layer 12 or the like. For example, the temperature of the electrolyte forming the release layer 12 is preferably 20° C. or higher and 60° C. or lower, and the pH is preferably 5.0 or more and 9.0 or less, and the current density is preferably 0.5 A/dm ² or more and 8 A/dm ² or less, and the treatment time is preferably 5 seconds or more and 40 seconds or less.

When the manufacturing conditions of the plating method are within the above range, Str and Rz which form the first main surface T12 and the second main surface B12 of the peeling layer 12 are slightly the same as Str and Rz of the second main surface B13 of the metal base material 13. Stripping layer 12. Further, since the first main surface T12 side of the peeling layer 12 can be formed mainly of an alloy and the second main surface B12 side is mainly a peeling layer made of an oxide, it has electrical conductivity. Thereby, the thin film metal 11 can be formed on the peeling layer 12 by electroplating in the third step.
(6.3) Third step

In the third step, as shown in FIG. 4C, a thin film metal foil 11 is formed on the peeling layer 12 by electroplating. Thereby, the second laminate 16 shown in Figs. 3C and 4D can be obtained.

Since the thin film metal foil 11 is directly formed on the peeling layer 12, the surface property of the second main surface B12 of the peeling layer 12 is transferred to the first main surface T11 of the thin film metal foil 11. Therefore, the thin metal foil 11 in which Str and Rz of the first main surface T11 of the thin film metal foil 11 are slightly the same as Str and Rz of the second main surface B12 of the peeling layer 12 can be formed. In other words, in the present embodiment, the second main surface B13 of the metal base material 13 and the thin metal foil 11 of the first main surface T11 of the thin film metal foil 11 which are slightly opposite to the peeling layer 12 can be formed.

The method of forming the thin film metal foil 11 is as shown in FIG. 4C. The metal substrate 13 is used as a cathode, and the first laminate 15 is immersed in the second electrolyte 131 in the second electrolyte tank 130 to form an anode. A current is passed between the cathode and the cathode, whereby the thin film metal foil 11 is electrodeposited onto the surface of the second main surface B13 side of the metal substrate 13 (the second main surface B12 of the peeling layer 12).

The second electrolyte solution 131 may be appropriately adjusted in accordance with the material constituting the thin film metal foil 11, and a copper sulfate plating bath, a copper cyanide plating bath, a copper fluoroborate plating bath, a copper pyrophosphate plating bath or an amine sulfonic acid may be used. Copper plating bath, etc.

The composition of the second electrolytic solution 131 may be appropriately adjusted in accordance with the material of the thin film metal foil 11 or the like. When the material of the thin film metal foil 11 is copper, the second electrolytic solution 131 preferably contains a copper compound, an acid, and a halogen monomer, and further contains a water-soluble solution. The polymer is preferred. The copper compound, the acid, the halogen monomer, and the water-soluble polymer may be the same as those contained in the first electrolyte 121. The second electrolyte solution 131 preferably contains the copper compound of 100 g/L or more and 300 g/L or less, the above-mentioned acid of 50 g/L or more and 150 g/L or less, and the halogen monomer of 1 mass ppm or more and 20 mass ppm or less. Further, the electrolyte solution 131 preferably contains a water-soluble polymer of 15 ppm or more and 35 ppm or less.

The production conditions of the film metal foil 11 may be appropriately adjusted in accordance with the material of the film metal foil 11 or the like. For example, the current density is preferably 1.0 A/dm ² or more and 10.0 A/dm ² or less, and the temperature of the second electrolytic solution 131 is preferably 10 ° C or more and 80 ° C or less, and the pH is preferably 5.0 or more and 9.0 or less.

The method of adjusting Str and Rz of the first main surface T11 of the thin film metal foil 11 to the above range may be such that the Str of the second main surface B13 of the metal base material 13 is adjusted to 0.5 or more and 1.0 or less and the first The Rz of the main surface T13 is adjusted to a range of 2.5 μm or less, and the thickness of the peeling layer 12 is adjusted so that the peeling layer 12 follows the surface property of the second main surface B13 of the metal substrate 13; and, the current density is adjusted and/or Or a method of immersing the drum in the electrolytic solution 131 and then flowing a current. The method of adjusting the thickness of the thin film metal foil 11 may be, for example, a method of adjusting the current density and/or the time during which the drum is immersed in the electrolytic solution 131 and the current flows.

Further, a copper base plating layer may be formed on the peeling layer 12 by an electroplating method, and then a thin film metal foil 11 may be formed on the copper underlying plating layer. Thereby, a more uniform plating can be applied to the peeling layer 12, so that the number of small holes of the film metal foil 11 can be remarkably reduced. A plating bath for forming a copper primer plating layer may be a copper pyrophosphate plating bath or a copper cyanide plating bath. The plating bath for forming the thin film metal foil 11 on the copper plating layer can be used, for example, a copper sulfate plating bath, a copper fluoroborate plating bath, a copper pyrophosphate plating bath, a copper sulfonate plating bath, and cyanidation. Copper plating bath. The thickness of the copper plating layer is preferably 0.001 μm or more and 1 μm or less. At this time, since the thickness of the copper plating layer is very thin, the surface property of the second main surface B12 of the peeling layer 12 is transferred to the first main surface T11 of the thin film metal foil 11, so that a thin film metal foil can be formed. The thin metal foil 11 of Str and Rz of the first main surface T11 of 11 is slightly the same as Str and Rz of the second main surface B12 of the peeling layer 12. Specifically, the second electrolyte 131 is preferably of the following composition.

The electrolyte for copper base plating preferably contains copper pyrophosphate, an alkali metal salt of pyrophosphoric acid and an alkaline substance. The basic substance may, for example, be sodium hydroxide, sodium hydrogencarbonate or ammonia. The electrolyte for copper base plating preferably contains 60 g/L or more and 120 g/L or less of the above copper pyrophosphate, 100 g/l or more and 400 g/L or less of the above alkali metal salt of pyrophosphoric acid, 0.1 ml/L. The above basic substance of 10 ml/L or less.

The manufacturing conditions of the plating method may be appropriately adjusted depending on the use of the thin film metal foil 11 or the like. For example, the temperature of the second electrolyte 131 is preferably 20° C. or higher and 80° C. or lower, the pH is preferably 6.0 or more and 9.0 or less, and the current density is preferably 0.5 A/dm ² or more and 10 A/dm ² or less, and the treatment time is preferably 1 More than seconds and less than 60 seconds.
(6.4) Blackening step

In the blackening step, the reflection-reducing layer 14 is formed on the second main surface B11 of the thin film metal foil 11. That is, the blackening treatment is performed on the second main surface B11 of the thin film metal foil 11. Thereby, the film metal foil 10 with the metal substrate shown in Figs. 1A and 3D can be obtained.

A method of forming the reflection reducing layer 14 may be, for example, an electroplating method. The plating bath used in the plating method may be appropriately adjusted in order to reduce the material of the reflective layer 14, and for example, a chromate plating or the like may be used.

Specifically, the plating bath used for the electroplating method preferably contains a metal compound and an acid. The above metallization may be a sulfate of a metal selected from copper, nickel, cobalt, tungsten or aluminum or an inorganic salt such as a nitrate or a chloride; or an acetate or an oxalate, a metal alkoxide or an acetamidine. An organic salt such as a acetonide salt; and a hydrate thereof. The above acids may, for example, be inorganic acids such as sulfuric acid, nitric acid or hydrochloric acid, and organic acids such as acetic acid, oxalic acid and dodecylbenzenesulfonic acid. The plating bath used in the plating method preferably contains the above-mentioned metal compound of 50 g/l or more and 300 g/L or less, and the above-mentioned acid of 10 g/L or more and 300 g/L or less.

The production conditions of the plating method may be appropriately adjusted depending on the use of the thin film metal foil 11, etc., and the temperature is preferably 10° C. or higher and 60° C. or lower, the current density is 1 A/dm ² or less, 50 A/dm ² or less, and the treatment time is 10 seconds or longer. Further, modulation is performed within 100 seconds, and a roughened layer composed of knob-shaped copper particles is formed on the second main surface B11 of the thin film metal foil 11.

Next, it is preferred to carry out chromate treatment on the surface after the formation of the roughened layer by using a plating bath containing 1.0 g/L or more and 10 g/L or less of sodium dichromate 2 hydrate.

The production conditions of the plating method may be appropriately adjusted depending on the use of the thin film metal foil 11, etc., and the pH is preferably 3.0 or more and 5.0 or less, and the liquid temperature is preferably 10 ° C or more and 50 ° C or less, and the current density is preferably 0.1 A/dm ² or more. 3.0A/dm ² or less.
(7) Method for producing a metal-clad transparent substrate material

The method for producing the metal-clad transparent substrate material 20 of the present embodiment includes a first step, a second step, a third step, a blackening step, a fourth step, and a fifth step. In the fourth step, the transparent substrate 21 is prepared, and a transparent adhesive layer is formed on both surfaces of the transparent substrate 21 to form a transparent substrate 23 with a transparent adhesive layer. In the fifth step, the surface B14 on the side of the thin film metal foil 11 of the metal foil with metal substrate is bonded to the surface of the transparent adhesive layer of the transparent substrate 23 to which the transparent adhesive layer is attached. The metal-coated transparent substrate material 20 can be obtained by following each step in the order of the first step, the second step, the third step, the blackening step, the fourth step, and the fifth step. In the present embodiment, the blackening step is included, but the present invention is not limited thereto, and the method of producing the metal-clad transparent substrate material 20 may not include the blackening step. In the present embodiment, a transparent adhesive layer is formed on both surfaces of the transparent substrate 21. However, the present invention is not limited thereto, and a transparent adhesive layer may be formed only on one surface of the transparent substrate 21.
(7.1) Fourth step

In the fourth step, the transparent substrate 21 is prepared, and a first transparent adhesive layer 22AU is formed on the first main surface T21 of the transparent substrate 21, and a second transparent surface is formed on the second main surface B21 of the transparent substrate 21. Next to the agent layer 22BU. Thereby, the transparent substrate 23 with the transparent adhesive layer shown in Fig. 5A can be obtained. The cured material of the first transparent adhesive layer 22AU is the first transparent adhesive layer 22A. The cured material of the second transparent adhesive layer 22BU is the second transparent adhesive layer 22B.

The method of forming the first transparent adhesive layer 22AU and the second transparent adhesive layer 22BU may be, for example, a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure.
(7.2) Fifth step

In the fifth step, the surface B14 on the first thin film metal foil 11A side of the first metal substrate-attached metal foil 10A and the first transparent adhesive layer 22AU on the transparent substrate 23 with the transparent adhesive layer are applied. T23 fits. Then, the surface B14 on the second thin film metal foil 11B side of the second metal substrate-attached metal foil 10B is bonded to the surface B23 of the second transparent adhesive layer 22BU of the transparent substrate 23 to which the transparent adhesive layer is attached. Thereby, the metal-clad transparent substrate material 20 shown in Figs. 1B and 5C can be obtained.

The bonding method can be exemplified by the following methods and the like. That is, as shown in FIG. 5B, the first transparent metal layer 11A on the first film metal foil 11A and the first transparent adhesive layer 23 on the transparent substrate 23 with the transparent adhesive layer are provided. The face T23 of the 22AU is opposite. Further, the surface B14 on the second thin film metal foil 11B side of the second metal substrate-attached metal foil 10B is opposed to the surface B23 of the second transparent adhesive layer 22BU of the transparent substrate 23 to which the transparent adhesive layer is attached. These are then integrated to harden the first transparent adhesive layer 22AU and the second transparent adhesive layer 22BU. Thereby, the first transparent adhesive layer 22AU is hardened to become the first transparent adhesive layer 22A. The second transparent adhesive layer 22BU is hardened to become the second transparent adhesive layer 22B.

The method of curing the first transparent adhesive layer 22AU and the second transparent adhesive layer 22BU may be appropriately adjusted according to the transparent adhesive constituting the first transparent adhesive layer 22AU and the second transparent adhesive layer 22BU, and may be used. A method in which a press or the like is heated under a predetermined pressure, a method of heating under a normal pressure or a low pressure environment, or the like.
(8) Method for manufacturing laminated plate for see-through electrode

The manufacturing method of the laminated electrode 30 for a see-through electrode includes a first step, a second step, a third step, a blackening step, a fourth step, a fifth step, and a sixth step. In the sixth step, the metal substrate and the release layer are peeled off from the metal-clad transparent substrate material 20. The laminated electrode laminated plate 30 can be obtained by following each step in the order of the first step, the second step, the third step, the blackening step, the fourth step, the fifth step, and the sixth step. In the present embodiment, the blackening step is included, but the present invention is not limited thereto, and the method of producing the metal-clad transparent substrate material 20 may not include the blackening step. In the present embodiment, a transparent adhesive layer is formed on both surfaces of the transparent substrate 21. However, the present invention is not limited thereto, and a transparent adhesive layer may be formed only on one surface of the transparent substrate 21.
(8.1) Sixth step

In the sixth step, the first release layer 12A, the first metal substrate 13A, the second release layer 12B, and the second metal substrate 13B are peeled off from the metal-clad transparent substrate material 20. Thereby, the laminate electrode 30 for a see-through type electrode shown in FIGS. 2A and 5D can be obtained. When the first metal base material 13A is peeled off, the first release layer 12A is peeled off from the first film metal foil 11A along with the first metal base material 13A. Similarly, when the second metal substrate 13B is peeled off, the second release layer 12B is peeled off from the second film metal foil 11B along with the second metal substrate 13B.
Example

The invention will be specifically described below by way of examples.

In the examples, the thicknesses of the Str, Rz and thin film metal foils were measured as follows.
[Measure Str]

The surface roughness was measured by using a measuring instrument ("laser microscope VK-X150" manufactured by KEYENCE CO., using a 50-fold lens), and measuring the Str of the film metal foil in accordance with ISO25178. The height distribution of the film metal foil in the measurement region of 274.70 μm × 210.00 μm was measured, and the measurement region was equally divided into four regions, and after the Str of each region was determined, the average value of the film was used as the surface property of the film metal foil. Aspect ratio (Str). Those with a Str of 0.5 or more and 1.0 or less are evaluated as "○", and those below 0.5 are evaluated as "X".
[Measure Rz]

Rz was measured with a stylus 2 μm by a stylus method in accordance with JIS B 0651 (1996) and JIS B 0601 (1994) using a surface roughness measuring instrument ("SURFCOM 1500SD" manufactured by Tokyo Seimi Co., Ltd.). The measurement range is 10 mm in a straight line. When Rz is 2.5 μm or less, it is evaluated as “○”, and when it exceeds 2.5 μm, it is evaluated as “×”.
[Measurement of thickness of metal substrate and film metal foil]

The thickness of the metal base material and the film metal foil was calculated by a weight method in which the weight of the copper foil cut into 10 cm square was measured and converted from a copper density of 8.96 g/cm ³ .
[Measure section length and height difference]

The cross-sectional length and the height difference were measured using a measuring instrument ("Ray Microscope VK-X100" manufactured by KEYENCE CO., using a 50-fold lens) to measure the height difference and the cross-sectional length L1 of the wiring pattern layer. The length L2 of the reference line 102 is set to 274.410 μm.

The height difference is as shown in FIG. 13, and after the wiring pattern layer 42 is cut in a vertical plane, the maximum top height Hp and the maximum height L3 with respect to the convex portion are calculated in the unevenness of the section curve 101 of the slit. The sum of the bottom depths Hv (height difference = Hp + Hv). The section length L1 is the length of the measurement section curve 101 as shown in FIG. Then, the ratio (L1/L2) with respect to the length L2 of the reference line 102 is calculated.
[Measure the number of broken wires in the wiring pattern layer]

After removing the thin film metal foil 11 of the single-sided see-through electrode laminated board 30S and the portion of the reflective layer 14 by photolithography, the disconnection inspection wiring pattern layer 42C having the pattern for disconnection inspection shown in FIG. 6 is obtained. Single-sided see-through electrode material 40C for wire breakage inspection. The number of disconnection of the disconnection inspection wiring pattern layer 42C of the single-sided see-through type electrode material 40C for the disconnection inspection is counted.
[Example 1]
[Production of film metal foil with metal substrate 10]
(Metal substrate 13)

A titanium rotating drum having a surface ground is prepared for the electrolytic drum 110. An electrolyte solution containing 170 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, 6 mass ppm of chlorine, and gelatin (average molecular weight: 2000) of 30 ppm was prepared for the first electrolyte solution 121.

As shown in FIG. 4A, the electrolytic drum 110 is used as a cathode, and the gantry having an arcuate cross section with respect to the electrolytic drum 110 is used as an anode, and the electrolytic drum 110 is immersed in the first electrolytic solution 121 in the electrolytic solution tank 120. Next, under the manufacturing conditions of a current density of 6.0 A/dm ² and a temperature of the first electrolyte 121 of 40 ° C, the electrolytic drum 110 is rotated to cause a current between the anode and the cathode to flow for 20 minutes, thereby being used in the electrolytic drum 110. Electrodeposited metal on the surface.

Next, the metal deposited on the surface of the electrolytic drum 110 is peeled off from the electrolytic drum 110 to continuously obtain the metal base material 13 shown in Fig. 3A. The obtained metal substrate 13 was cleaned by a cathode treatment in a 10% sulfuric acid at a temperature of 30 ° C, a current density of 5 A/dm ² and a treatment time of 20 seconds, and then washed with pure water for 20 seconds.

The surface properties and thickness of the metal substrate 13 after washing were measured. The metal substrate 13 has a thickness of 17 μm. The surface property of the second main surface B13 of the side of the metal base material 13 which is not in contact with the electrolytic drum 110 is such that Str is 0.733 and Rz is 1.383 μm. The surface property of the first main surface T13 (light surface) on the side of the metal substrate 13 that is in contact with the electrolytic drum 110 is such that Str is 0.261 and Rz is 1.637 μm.
(peeling layer 12)

The metal substrate 13 was immersed in _{30g / L, Na 2 MoO 4} 2 dihydrate 3g / L, sodium citrate 40g / L of the release layer comprising nickel sulfate 6 hydrate forming electrolyte at a temperature of 30 ℃, pH Electrolysis was carried out under the conditions of a current density of 2 A/dm ² and a treatment time of 20 seconds. The release layer 12 was formed on the second main surface B13 of the metal substrate 13, and then washed with running water for 20 seconds. Thereby, the first laminate 15 shown in Fig. 3B is obtained. The first main surface T12 side of the peeling layer 12 mainly contains an alloy of nickel and molybdenum, and the second main surface B12 side mainly contains an oxide of nickel and molybdenum.
(film metal foil 11)

The first laminate 15 was immersed in a copper pyrophosphate plating bath containing copper pyrophosphate 80 g/L, potassium pyrophosphate 320 g/L, and ammonia water 2 ml/L at a temperature of 40 ° C, a pH of 8.5, and a current density of 2.0. After performing a cathodic treatment with A/dm ² and a treatment time of 20 seconds, it was washed with pure water for 20 seconds.

Next, the first laminate 15 is immersed in an electrolyte solution for forming a thin film metal foil containing 160 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, gelatin (weight average molecular weight: 5000) of 15 ppm, and chloride ion of 5 ppm. After electrolysis was carried out at 40 ° C, a pH of 7, a current density of 3.5 A/dm ² , and a treatment time of 150 seconds, a thin film metal foil 11 was formed on the second main surface B12 of the peeling layer 12. Thereby, the second laminate 16 shown in Fig. 3C is obtained.

Next, the second laminate 16 was washed with running water for 20 seconds. The thickness of the film metal foil 11 of the second laminate 16 after the washing was measured to obtain 2 μm. Next, the second laminate 16 is subjected to rustproof treatment and decane coupling agent treatment.
(reducing the reflective layer 14)

The second laminate 16 was immersed in an electrolytic solution containing 30 g/L of copper sulfate monohydrate and 20 g/L of sulfuric acid, and electrolyzed at a temperature of 80 ° C, a current density of 7 A/dm ² , and a treatment time of 20 seconds. A roughened layer of copper is formed on the second main surface B11 of the thin film metal foil 11. Next, the second laminate 16 on which the copper rough layer was formed was immersed in a chromate bath containing sodium dichromate 2 hydrate 3.5 g/L at a temperature of 30 ° C, a pH of 4.0, and a current density. The chromate treatment was carried out under conditions of 0.5 A/dm ² and a treatment time of 2.5 seconds. Thereby, the film metal foil 10 with the metal substrate shown in Fig. 3D is obtained.

Next, the metal base material 13 was peeled off from the film metal foil 10 with a metal base material, and the peeling surface was observed by SEM. When the metal base material 13 is peeled off, the peeling layer 12 is peeled off from the film metal foil 11 along with the metal base material 13. The SEM image (magnification: 1000 times) of the first main surface T11 of the thin film metal foil 11 as the peeling surface on the side of the thin film metal foil 11 is shown in the figure after the metal base material 13 is peeled off from the metal foil 10 of the metal base material. 7A.
[Production of single-sided metal-coated transparent substrate material 20S]

A highly transparent PET film ("COSMOSHINE A4300" manufactured by Toyobo Co., Ltd., thickness: 100 μm) was prepared for the transparent substrate 21. The transparent adhesive (urethane resin) prepared by the following composition was applied onto the first main surface T21 of the transparent substrate 21 at a coating amount of 3 g/m ² , and then kept at 100 ° C for 5 minutes. It was dried to form a first transparent adhesive layer 22AU having a thickness of 7 μm. Thereby, the transparent substrate 23S having the one-side transparent adhesive layer shown in Fig. 8A was obtained.
(composition of transparent adhesive)
Main agent: "Dynaleo VA-3020" manufactured by TOYO INK CO., LTD.
Hardener: "Dynaleo HD-701" manufactured by TOYO INK CO., LTD.
Mass ratio: main agent / hardener = 100/7

The first transparent adhesive layer 22AU of the transparent substrate 23S with the transparent adhesive layer on one side and the lower reflective layer 14 of the thin metal foil 10 with the metal substrate are opposite to each other as shown in FIG. 8B, and the single side is transparent. The transparent substrate 23S of the subsequent layer and the thin film metal foil 10 with the metal substrate are laminated and bonded. The bonded state was maintained at 60 ° C for 5 days, and the first transparent adhesive layer 22 AU was cured to form the first transparent adhesive layer 22A. Thereby, the single-sided metal-clad transparent substrate material 20S shown in Fig. 8C is obtained.
[Production of single-sided see-through electrode laminate board 30S]

The metal base material 13 and the peeling layer 12 are peeled off from the single-sided metal-clad transparent base material 20S. Thereby, the single-layer see-through type electrode laminated board 30S shown in FIG. 8D is obtained. At this time, when the metal base material 13 is peeled off, the peeling layer 12 is peeled off from the film metal foil 11 along with the metal base material 13. The surface property of the first main surface T11 of the thin film metal foil 11 of the laminated plate 30S for single-sided see-through electrodes was obtained, and Str was 0.781 and Rz was 1.630 μm.
[Making single-sided see-through electrode material]

After the film metal foil 11 of the single-sided see-through electrode laminate 30S and a portion of the reflective layer 14 are removed by photolithography, a line/space (L/S)=5 μm/1000 μm is obtained. Single-sided see-through electrode material of a wiring pattern layer of a lattice mesh pattern. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 291.235 μm, and L1/L2 was 1.06. And the height difference is 1.512μm. The wiring pattern layer of the single-sided see-through electrode material was observed by SEM. The SEM image (magnification: 2000 times) of the wiring pattern layer is shown in FIG. 9A. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 0.0 pieces/m ^{2 were obtained} .
[Modification 1]

In the transparent substrate 21 of Example 1, a cycloolefin film (ZF-160 (thickness: 100 μm) manufactured by ZEON, Japan) was used in place of the highly transparent PET film, and both surfaces were subjected to corona discharge treatment, and a transparent adhesive (amine) was applied. A single-sided see-through electrode laminate 30S was obtained in the same manner as in Example 1 except that the ethyl formate resin was used. Further, a single-sided see-through type electrode material was produced from the obtained single-sided see-through electrode laminate 30S. The surface property of the first main surface T11 of the thin film metal foil 11 of the laminated plate 30S for single-sided see-through electrodes was obtained, and Str was 0.890 and Rz was 2.202 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 296.500 μm, and L1/L2 was 1.08. And the height difference is 1.797 μm. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 0.0 pieces/m ^{2 were obtained} . Further, the image display device 53 shown in FIG. 2C uses a liquid crystal display panel, and the device 50 can observe the rainbow light spot on the single-sided see-through electrode material obtained in the first embodiment, and the rainbow spot can be observed. After the single-sided see-through type electrode material of Example 1 was replaced with the single-sided see-through type electrode material obtained in Modification 1, no rainbow spot was observed.
[Modification 2]

A single-sided see-through electrode was produced in the same manner as in Example 1 except that a super-birefringent polyester film (SRF (thickness: 80 μm) manufactured by Toyobo Co., Ltd.) was used instead of the highly transparent PET film in the transparent substrate 21 of the first embodiment. Laminate 30S. Further, a single-sided see-through type electrode material was produced from the obtained single-sided see-through electrode laminate 30S. The surface property of the first main surface T11 of the thin film metal foil 11 of the laminated plate 30S for single-sided see-through electrodes was obtained, and Str was 0.844 and Rz was 2.111 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 289.654 μm, and L1/L2 was 1.06. And the height difference is 1.894 μm. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 0.0 pieces/m ^{2 were obtained} . Further, the image display device 53 shown in FIG. 2C uses a liquid crystal display panel to observe the screen of the device 50 with respect to the single-sided see-through type electrode material of the first embodiment through the polarized sunglasses, and can observe the rainbow spot, and according to the viewing. The blackout phenomenon can be observed at the angle of the screen. However, when the single-sided see-through electrode material of the first embodiment is replaced with the single-sided see-through electrode material of the second modification, neither the rainbow spot nor the blackout phenomenon is observed. To.
[Embodiment 2]

When the metal substrate 13 is produced, the composition of the first electrolyte solution 121 is set to contain 270 g/L of copper sulfate pentahydrate, 90 g/L of sulfuric acid, 20 mass ppm of chlorine, and polyethylene glycol (average molecular weight of 1000) of 10 ppm. a composition of 5 ppm of 3-mercapto-1-propanesulfonic acid, and plating conditions were set to a current density of 50 A/dm ² , a temperature of the first electrolyte 121 of 40 ° C, and a plating time of 2 minutes, in addition to In the same manner as in the first embodiment, a single-sided see-through electrode laminate 30S was obtained, and a single-sided see-through type electrode material was obtained from the obtained single-sided see-through electrode laminate 30S. The surface property of the first main surface T11 of the thin film metal foil 11 of the laminated plate 30S for single-sided see-through electrodes was obtained, and Str was 0.634 and Rz was 1.383 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 286.818 μm, and L1/L2 was 1.05. And the height difference is 1.397μm. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 3.3 pieces/m ^{2 were obtained} .
[Example 3]

When the metal substrate 13 is produced, the composition of the first electrolyte solution 121 is set to contain 280 g/L of copper sulfate pentahydrate, 90 g/L of sulfuric acid, 10 mass ppm of chlorine, and polyethylene glycol (average molecular weight of 1000): 10 ppm. , 3-mercapto-1-propanesulfonic acid: a composition of 1 ppm, and the plating conditions were set to a current density of 50 A/dm ² , the temperature of the first electrolyte 121 was 40 ° C, and the plating time was 2 minutes, except In the same manner as in the first embodiment, a single-sided see-through electrode laminate 30S was obtained, and a single-sided see-through type electrode material was obtained from the obtained single-sided see-through electrode laminate 30S. The surface property of the first main surface T11 of the thin film metal foil 11 of the laminated plate 30S for single-sided see-through electrodes was obtained, and Str was 0.856 and Rz was 2.199 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 293.647 μm, and L1/L2 was 1.07. And the height difference is 1.807 μm. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 0.0 pieces/m ^{2 were obtained} .
[Comparative Example 1]
[Production of film metal foil 203 with metal substrate]
(metal substrate 210)

The metal base shown in Fig. 10A was continuously produced in the same manner as in Example 1 except that the composition of the first electrolytic solution 121 was changed to a composition containing 160 g/L of copper sulfate pentahydrate, 100 g/L of sulfuric acid, and 5 ppm of chloride ions. Material 210.

The obtained metal substrate 210 was cleaned with pure water in a 10% sulfuric acid at a temperature of 30 ° C, a current density of 5 A/dm ² and a treatment time of 20 seconds, and then washed with pure water for 20 seconds.

The surface properties and thickness of the washed metal substrate 210 were measured. The thickness of the metal substrate 210 was 2.1 μm. The surface property of the first main surface T210 (light surface) on the side of the metal substrate 210 that is in contact with the electrolytic drum 110 is such that Str is 0.482 and Rz is 1.713 μm.
(peeling layer 220)

The peeling layer 220 was formed on the first main surface T210 of the metal substrate 210 under the same conditions as in Example 1, and then washed with running water for 20 seconds. Thereby, the third laminate 201 shown in Fig. 10B is obtained.
(film metal foil 230)

The thin film metal foil 230 was formed on the first main surface T220 of the peeling layer 220 under the same conditions as in the first embodiment. Thereby, the fourth laminate 202 shown in Fig. 10C is obtained.

The fourth laminate 202 was then washed with running water for 20 seconds. The thickness of the film metal foil 230 of the fourth laminate 202 after washing was measured to obtain 2 μm.
(rustproof treatment layer and decane coupling treatment layer)

The rustproof treatment and the decane coupling agent treatment were carried out under the same conditions as in Example 1.
(reducing the reflective layer 240)

A thin Ni layer was formed on the first main surface T230 of the thin film metal foil 230 under the same conditions as in Example 1. Thereby, the film metal foil 203 with the metal substrate shown in Fig. 10D is obtained.

The film metal foil 203 of the obtained metal substrate was used to lower the surface property of the first main surface T240 of the reflective layer 240, and Str was 0.380 and Rz was 1.657 μm.

After peeling off the metal base material 210 from the film metal foil 203 with a metal base material, the peeling surface was observed by SEM. When the metal substrate 210 is peeled off, the peeling layer 220 is peeled off from the film metal foil 230 along with the metal substrate 210. The SEM image (magnification: 1000 times) of the second main surface B230 of the thin film metal foil 230 which is the peeling surface of the film metal foil 230 side is shown in the figure after peeling the metal base material 210 from the metal foil 203 of the metal base material. 7B.
[Production of single-sided metal-clad transparent substrate material 204]

A transparent substrate 23S having a single-sided transparent adhesive layer as shown in Fig. 10E was obtained in the same manner as in Example 1.

The first transparent adhesive layer 22AU of the transparent substrate 23S with the transparent adhesive layer on one side and the lower reflective layer 240 of the thin metal foil 203 of the metal-attached substrate are opposite to each other as shown in FIG. 10F, and the single side is transparent. The transparent substrate 23S of the subsequent layer and the film metal foil 203 with the metal substrate are laminated and bonded. The bonded state was maintained at 60 ° C for 5 days, and the first transparent adhesive layer 22 AU was cured to form the first transparent adhesive layer 22A. Thereby, the single-sided metal-clad transparent substrate material 204 shown in Fig. 10G is obtained.

Next, the metal base material 210 and the peeling layer 220 are peeled off from the single-sided metal-clad transparent base material 204. Thereby, the single-sided see-through electrode laminate board 200 shown in FIG. 10H is obtained. At this time, when the metal base material 210 is peeled off, the peeling layer 220 is peeled off from the film metal foil 230 along with the metal base material 210. The surface property of the second main surface B230 of the film metal foil 230 of the laminated plate 200 for a single-sided see-through electrode was obtained, and Str was 0.461 and Rz was 2.449 μm.
[Making single-sided see-through electrode material]

After the film metal foil 230 of the single-sided see-through electrode laminate 200 and one portion of the reflective layer 240 are removed by photolithography in the same manner as in the first embodiment, a line width/line pitch (L/S) = 5 μm/ is obtained. Single-sided see-through electrode material of a wiring pattern layer of a lattice pattern of 1000 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 316.280 μm, and L1/L2 was 1.15. And the height difference is 2.409μm. The wiring pattern layer of the single-sided see-through electrode material was observed by SEM. The SEM image (magnification: 2000 times) of the wiring pattern layer is shown in FIG. 9B. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 10.0 pieces/m ^{2 were obtained} .
[Comparative Example 2]

In the same manner as in Comparative Example 1, a single-sided see-through type was produced in the same manner as in Comparative Example 1, except that the polishing conditions of the electrolytic drum 110 were changed to be the same as in Comparative Example 1 except that Str of the first main surface T210 (light surface) of the metal substrate 210 was 0.348 and Rz was 1.607 μm. The electrode laminated board 200 was used to obtain a single-sided see-through type electrode material from the obtained single-sided see-through electrode laminated board 200. The surface property of the second main surface B230 of the film metal foil 230 of the laminated plate 200 for a single-sided see-through electrode was obtained, and Str was 0.380 and Rz was 1.657 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through electrode material was 313.110 μm, and L1/L2 was 1.14. And the height difference is 2.672μm. As a result of confirming whether or not the disconnection inspection wiring pattern layer 42C was broken, 6.6 pieces/m ^{2 were obtained} .
[Comparative Example 3]

In the same manner as in Comparative Example 1, a single-sided see-through type was produced in the same manner as in Comparative Example 1, except that the polishing conditions of the electrolytic drum 110 were changed so that the Str of the first main surface T210 (light surface) of the metal base material 210 was 0.220 and Rz was 2.351 μm. The electrode laminated board 200 was used to obtain a single-sided see-through type electrode material from the obtained single-sided see-through electrode laminated board 200. The surface property of the second main surface B230 of the thin film metal foil 230 of the laminated plate 200 for single-sided see-through electrodes was obtained, and Str was 0.237 and Rz was 1.632 μm. The cross-sectional length L1 of the wiring pattern layer of the obtained single-sided see-through type electrode material was 309.559 μm, and L1/L2 was 1.013. And the height difference is 3.826μm. The result of confirming whether or not the wiring pattern layer was broken was 6.6 pieces/m ² .
[Comparative Example 4]

When the metal substrate 13 was produced, a single-sided see-through electrode laminate board 200 was produced in the same manner as in Example 1 except that the plating time of <plating conditions> was changed to 40 minutes. After the film metal foil 230 of the obtained single-sided see-through electrode laminate 200 and a portion of the reflection-reducing layer 240 were removed by photolithography in the same manner as in Example 1, the line width/space distance (L/S) was not formed. A wiring pattern layer of a lattice pattern of 5 μm/1000 μm. It is also impossible to form the wire harness inspection wiring pattern layer 42C. The surface property of the second main surface B230 of the thin film metal foil 230 of the laminated plate 200 for single-sided see-through electrodes was obtained, and Str was 0.728 and Rz was 3.740 μm.
[Comparative Example 5]

A single-sided see-through electrode was produced in the same manner as in Comparative Example 1, except that the polishing conditions of the electrolytic drum 110 were changed so that the first main surface T210 (light surface) of the metal substrate 210 had a Str of 0.380 and an Rz of 3.835 μm. The laminate board 200. After the film metal foil 230 of the obtained single-sided see-through electrode laminate 200 and a portion of the reflection-reducing layer 240 were removed by photolithography in the same manner as in Example 1, the line width/space distance (L/S) was not formed. A wiring pattern layer of a lattice pattern of 5 μm/1000 μm. It is also impossible to form the wire harness inspection wiring pattern layer 42C. The surface property of the second main surface B230 of the film metal foil 230 of the laminated plate 200 for a single-sided see-through electrode was obtained, and Str was 0.325 and Rz was 3.890 μm.

Str and Rz of the first main surface T11 of the laminated plate 30S for single-sided see-through electrodes and the second main surface B230 of the laminated plate 200 for single-sided see-through electrodes, and a cross section of the wiring pattern layer of the single-sided see-through type electrode material The results of the measurement of length, height difference and presence or absence of breakage are shown in Table 1.

[Table 1]

[Reference example]

The transmission loss of the sample 310 described below was evaluated in the following manner.

A high smooth copper foil (35), a general copper foil (35), a high smooth copper foil (18), and a general copper foil (18) were prepared for the sample 310. The copper foil thicknesses T ₃₁₀ , Str, Ra, Rz and the cross-sectional length L1 of each sample 310 are shown in Table 2. The surface properties of both sides of each sample 310 can be evaluated as the same. The length L2 of the reference line 102 of the section length L1 is 274.410 μm. Further, the L1/L2 of each sample, the high smooth copper foil (35) was 1.06, the general copper foil (35) was 1.13, the high smooth copper foil (18) was 1.04, and the general copper foil (18) was 1.13.

[Table 2]

As shown in FIG. 11 , the short-stack sample 310 having the line width W is sandwiched by two prepregs (thickness: 0.06 mm) so that the impedance is 50 Ω, and then the copper foil 320 is disposed on the surface of each prepreg. T ₃₂₀ : 35 μm), and the whole was heat-pressed to harden the prepreg. Thereby, a copper clad laminate 300 having a strip line is produced. As for the sample 310, a sample 310 is embedded in a center position in the thickness direction of the insulating layer 330 (thickness T330: 0.28 mm). The line length is 1m. The strip line has an impedance of 50 Ω. Further, the sample 310 was not subjected to blackening treatment.

In the state where the outermost copper foils 320 and 320 are grounded, AC power of 2.0 GHz, 3.5 GHz, or 5.0 GHz is transmitted to the sample 310, and "N5230A 4 埠 PNA-L network analyzer 13.5/20 GHz manufactured by KEYSIGHTTECHNOLOGIES Co., Ltd. is used. Measure transmission loss. The results are shown in Table 3 and Figure 12.
[table 3]

From the results shown in Table 3 and Figure 12, the transmission loss of the high smooth copper foil (35) is the same as the transmission loss of the high smooth copper foil (18) at each frequency, and the transmission loss of the general copper foil (35) is generally The transmission loss of the copper foil (18) is the same. Further, as shown in FIG. 12, as the frequency of the alternating current increases, the transmission loss of the high smooth copper foil (35) or the high smooth copper foil (18) and the transmission loss of the general copper foil (35) or the general copper foil (18) The gap between them has also increased. From these results, it is understood that the copper foil thickness T _{310 of the} sample ₃₁₀ does not greatly affect the transmission loss in the high frequency band region of 2 GHz or more, and the cross-sectional length of the sample 310 greatly affects the transmission loss. Further, it is also known that the sample 310 having a short cross-sectional length has less transmission loss than the sample 310 having a longer cross-sectional length. Therefore, it is assumed that the first main surface T11 of the thin film metal foil 11 of the present embodiment has a high smooth surface and the cross-sectional length is shorter than that of the conventional ultra-thin copper foil, so that transmission loss is small particularly in a high-frequency band region. .

10‧‧‧Metal foil with metal substrate

10A‧‧‧First film metal foil with metal substrate

10B‧‧‧Second film metal foil with metal substrate

11‧‧‧Metal foil

11A‧‧‧First film metal foil

11B‧‧‧Second film metal foil

12‧‧‧ peeling layer

12A‧‧‧First peeling layer

12B‧‧‧Second stripping layer

13‧‧‧Metal substrate

13A‧‧‧First metal substrate

13B‧‧‧Second metal substrate

14‧‧‧Reducing the reflective layer

14A‧‧‧First reduced reflection layer

14B‧‧‧Second lower reflection layer

15‧‧‧First laminate

16‧‧‧Second laminate

20‧‧‧Metal coated transparent substrate material

20S‧‧‧Single metal coated transparent substrate material

21‧‧‧Transparent substrate

22A‧‧‧First transparent layer

22B‧‧‧Second transparent layer

22AU‧‧‧first transparent adhesive layer

22BU‧‧‧Second transparent adhesive layer

23‧‧‧Transparent substrate with transparent adhesive layer

23S‧‧‧ Transparent substrate with a transparent adhesive layer on one side

30‧‧‧Surface electrode for laminated electrodes

30S‧‧‧ single-sided perspective electrode laminate

40‧‧‧Perspective electrode material

40C‧‧‧Single-sided perspective electrode material for wire break inspection

41‧‧‧Reducing the reflective pattern layer

41A‧‧‧First reduced reflection pattern layer

41B‧‧‧Second lower reflection pattern layer

42‧‧‧Wiring pattern layer

42A‧‧‧First wiring pattern layer

42B‧‧‧Second wiring pattern layer

42C‧‧‧Wiring pattern layer for wire break inspection

50‧‧‧Devices

51‧‧‧Control wiring

52‧‧‧ Cover

53‧‧‧Image display device

100‧‧‧ copper foil sample

101‧‧‧ section curve

102‧‧‧ baseline

110‧‧‧ Electrolytic roller

120‧‧‧ electrolyte tank

121‧‧‧First electrolyte

130‧‧‧Second electrolyte tank

131‧‧‧Second electrolyte

200‧‧‧Single-sided perspective electrode laminate

201‧‧‧ Third laminate

202‧‧‧fourth laminate

203‧‧‧Metal foil with metal substrate

204‧‧‧Single metal coated transparent substrate material

210‧‧‧Metal substrate

220‧‧‧ peeling layer

230‧‧‧Metal foil

240‧‧‧Reducing the reflective layer

300‧‧‧Copper laminate

310‧‧‧ samples

320‧‧‧ copper foil

330‧‧‧Insulation

A22A‧‧‧First Appearance

A22B‧‧‧Second Appearance

A40A‧‧‧ first opening

A40B‧‧‧ second opening

B11‧‧‧ second main surface of film metal foil

B12‧‧‧Second main surface of the peeling layer

B13‧‧‧ second main surface of metal substrate

B14‧‧‧Reducing the second main surface of the reflective layer (Fig. 1), the second main surface of the transparent adhesive layer (Fig. 2A), and the surface of the first thin film metal foil of the first metal substrate with the metal substrate ( Figure 5B), the second film metal foil side of the second metal substrate with a metal foil (Fig. 5B)

B21‧‧‧Second main surface of transparent substrate

B23‧‧‧ Face of the second transparent adhesive layer of the transparent substrate with the transparent adhesive layer

B42‧‧‧Second main surface of the first/second wiring pattern layer

B230‧‧‧ second main surface of film metal foil

Hp‧‧‧Maximum height

Hv‧‧‧Maximum bottom depth

L1‧‧‧ section length

L2‧‧‧ baseline length

L3‧‧‧ average height of the convex part

The first main face of T11‧‧‧ film metal foil

The first major surface of the T12‧‧‧ peeling layer

The first main surface of the T13‧‧‧ metal substrate

T14‧‧‧Reducing the first major surface of the reflective layer

The first major surface of the T21‧‧‧ transparent substrate

T23‧‧‧ Face of the first transparent adhesive layer of the transparent substrate with a transparent adhesive layer

T53‧‧‧ display surface

The first major surface of the T210‧‧‧ metal substrate

The first major surface of the T220‧‧‧ peeling layer

The first main surface of T230‧‧‧ film metal foil

T240‧‧‧Reducing the first major surface of the reflective layer

T310, T320‧‧‧ copper foil thickness

T330‧‧‧Insulation thickness

W‧‧‧Line width

W1‧‧‧ opening width

Fig. 1 is a schematic cross-sectional view showing a thin film copper foil with a metal substrate according to an embodiment of the present invention in a thickness direction. Fig. 1B is a schematic cross-sectional view showing a metal-coated transparent substrate material in a thickness direction according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing a laminated plate for a see-through electrode according to an embodiment of the present invention in the thickness direction. Fig. 2B is a schematic cross-sectional view showing a perspective type electrode material according to an embodiment of the present invention in a thickness direction. Fig. 2C is a schematic cross-sectional view showing the device in the thickness direction according to the embodiment of the present invention.

3A to 3D are schematic explanatory views showing respective steps of a method for producing a film-attached copper foil with a metal substrate according to an embodiment of the present invention.

Fig. 4 is a schematic cross-sectional view for explaining a method of manufacturing a metal substrate by an electrolytic method of an electrolytic drum according to an embodiment of the present invention. 4B is an enlarged cross-sectional view of the metal substrate in the portion D of FIG. 4A. 4C is a schematic explanatory view for explaining a method of manufacturing the second laminate. Figure 4D is an enlarged cross-sectional view of the second laminate in position E of Figure 4C.

5A to 5D are schematic explanatory views showing respective steps of a method of manufacturing a laminated electrode for a see-through electrode according to an embodiment of the present invention.

Fig. 6 is a plan view showing a pattern for wire breakage inspection of the single-sided see-through type electrode material for wire breakage inspection.

In Fig. 7, Fig. 7A is a scanning electron microscope (SEM) of the first main surface of the thin film metal foil as a peeling surface of the thin metal foil side after peeling the metal substrate from the thin metal foil of the metal substrate of Example 1. : Scanning Electron Microscope image (observation magnification: 1000 times). 7B is an SEM image (observation magnification: 1000 times) of the second main surface of the film metal foil as a release surface of the film metal foil side after the metal substrate was peeled off from the film metal foil of the metal substrate of Comparative Example 1.

8A to 8D are schematic explanatory views showing respective steps of a method of manufacturing a single-layer see-through electrode laminate according to the first embodiment.

In Fig. 9, Fig. 9A is an SEM image (observation magnification: 2000 times) of the wiring pattern layer of the single-sided see-through electrode material of Example 1. 9B is an SEM image (observation magnification: 2000 times) of the wiring pattern layer of the single-sided see-through electrode material of Comparative Example 1.

10A to 10H are schematic explanatory views showing respective steps of a method of manufacturing a laminated sheet for a single-sided see-through type electrode of Comparative Example 1.

Fig. 11 is a schematic cross-sectional view showing a printed wiring board having a strip line in a thickness direction in a reference example.

Fig. 12 is a graph showing the results of measurement of the transmission loss of each sample of the reference example.

Fig. 13 is a cross-sectional view showing the wiring of the height difference and the section length.

Claims (20)

A thin film metal foil with a metal substrate, characterized by: a thin film metal foil having a first major surface and a second major surface; a peeling layer provided on the first main surface and having conductivity; and a metal substrate disposed on the peeling layer; The first main surface of the thin film metal foil has fine concavities and convexities having a ten-point average roughness (Rz) of 2.5 μm or less, and the aspect ratio (Str) of the surface properties of the first main surface is 0.5 or more and 1.0 or less. The film metal foil of the metal base material according to claim 1, wherein the difference in height of the fine concavities and convexities on the first main surface of the thin film metal foil is 2.3 μm or less. The thin film metal foil of the metal substrate according to claim 1 or 2, wherein a cross-sectional length of the first main surface of the thin film metal foil is 1.10 times or less with respect to a reference line length. The thin film metal foil of the metal substrate according to claim 1 or 2, wherein the thickness of the thin film metal foil is 0.1 μm or more and 5.0 μm or less. The film metal foil of the metal substrate according to claim 1 or 2, wherein the film metal foil contains at least one selected from the group consisting of copper, nickel, aluminum, and silver. The film metal foil of the metal substrate of claim 5, wherein the film metal foil contains copper in an amount of 80% by mass or more based on the total mass of the film metal foil. The thin film metal foil of the metal substrate according to claim 1 or 2, wherein the metal substrate contains 80% by mass or more of the total mass of the metal substrate, and is selected from the group consisting of copper, nickel, aluminum, magnesium, and tungsten. One of a group consisting of molybdenum, platinum, gold, and palladium. The film metal foil of the metal substrate according to claim 1 or 2, wherein the metal substrate has a thickness of 7 μm or more and 40 μm or less. The thin film metal foil of the metal substrate of claim 1 or 2, wherein the second main surface of the thin film metal foil is provided with a reflection reducing layer. A metal-coated transparent substrate material characterized by having: Transparent substrate; The film metal foil of the metal substrate of claim 1 which is provided on one or both sides of the transparent substrate; A transparent adhesive layer between the transparent substrate and the aforementioned thin film metal foil. The metal-coated transparent substrate material of claim 10, wherein the transparent adhesive layer comprises an acrylic resin, an epoxy resin, an urethane resin, or a mixed resin thereof. The metal-coated transparent substrate material of claim 10 or 11, wherein the transparent adhesive layer has a hardness of 1.0 N/mm ² or more and 200 N/mm ² or less. The metal-coated transparent substrate material of claim 10 or 11, wherein the transparent substrate comprises a cycloolefin film having a retardation value of 100 nm or less or a polyester film having a retardation value of 3000 nm or more. A laminated electrode for a see-through electrode, characterized in that the metal substrate and the release layer are peeled off from the metal-coated transparent substrate material of claim 10 or 11. A see-through electrode material comprising a wiring pattern layer having the opening of the thin film metal foil of the see-through electrode laminate according to claim 14. The see-through electrode material of claim 15, wherein a line width of the wiring pattern layer is 0.5 μm or more and 10 μm or less, or an opening width of 50 μm or more and 10000 μm or less. The perspective electrode material of claim 16 has a sheet resistance of 0.01 Ω/sq or more and 50 Ω/sq or less. The see-through electrode material of claim 16 has a total light transmittance of 60% or more. A device characterized by having: a see-through electrode material as claimed in claim 15; A control circuit that has been electrically connected to the aforementioned wiring pattern layer. A see-through electrode material having: Transparent substrate; and a wiring pattern layer formed on one surface or both surfaces of the transparent substrate and having a thickness of 0.1 μm or more and 5.0 μm or less; The wiring pattern layer is formed by patterning a thin film metal foil bonded to the transparent substrate via a transparent adhesive layer, and The ten-point average roughness (Rz) of the surface of the wiring pattern layer is 2.5 μm or less, and the aspect ratio (Str) of the surface property of the surface of the wiring pattern layer is 0.5 or more and 1.0 or less.