JPWO2015178455A1 - Copper foil for transparent resin substrate and transparent resin substrate with fine copper wiring - Google Patents

Abstract

The subject of this invention is the copper foil for transparent resin base materials, and fine wiring suitable when forming the very fine copper wiring with high scratch resistance and acid-soluble property on the surface of a transparent resin base material, and high antireflection effect It is providing the manufacturing method of a transparent resin base material with an attachment and a transparent resin base material with fine wiring. In order to solve the above problems, as a copper foil for a transparent resin base material for forming a copper wiring on the surface of a transparent resin base material, the surface of the copper foil contains cuprous oxide and cupric oxide, these A copper foil for a transparent resin substrate comprising a fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound Use.

Description

  The present invention relates to a copper foil for a transparent resin substrate and a transparent resin substrate with a fine copper wiring, and in particular, a copper foil for a transparent resin substrate and a transparent with a fine copper wiring suitable for manufacturing materials for a fine wiring type transparent electrode such as a touch panel. The present invention relates to a resin base material.

  Conventionally, touch panels have been widely adopted as input devices for portable electronic devices such as mobile phones such as smartphones and portable game machines. In recent years, touch panels have come to be used as input devices for electronic devices having a relatively large display size such as tablet terminals and personal computers, and the area of touch panels has been increasing. In a capacitive touch panel such as a smartphone, a transparent electrode mainly using an ITO (indium tin oxide) electrode material has been used to detect a change in electrostatic capacitance on the surface. With the increase in area, it has been proposed to use a fine wiring type transparent electrode in which a fine wiring pattern made of a metal such as copper is provided on the surface of a transparent resin film. This is because the fine wiring type transparent electrode has a smaller surface resistance than the ITO electrode, and it is easy to increase the area of the touch panel.

  As such a fine wiring type transparent electrode, Patent Document 1 provides a striped copper wiring with equal intervals extending in the X direction on one side of a polyethylene terephthalate (hereinafter abbreviated as “PET”) film. On the other surface, there is disclosed a fine wiring type transparent electrode (mesh electrode) provided with striped copper wirings of equal intervals extending in the Y direction intersecting with the X direction. Conventionally, in this type of fine wiring type electrode, two sets of electrode materials having striped copper wiring extending in a predetermined direction are prepared on one side of a PET film, and the electrode materials are laminated so that the respective striped copper wirings intersect each other. Proposed fine wiring type transparent electrodes have been proposed. Compared with this conventional fine wiring type transparent electrode, the fine wiring type transparent electrode described in Patent Document 1 reduces the number of layers of the PET film from two to one by providing striped copper wiring on both sides of the PET film. can do. For this reason, the transmittance | permeability of visible light of a fine wiring type transparent electrode can be made higher than before, and also a man-hour and cost can be reduced.

  Moreover, in the fine wiring type transparent electrode described in Patent Document 1, in the striped copper wiring, black copper oxide is respectively formed on the surface that is visible to the user when the fine wiring type transparent electrode is mounted on the display. A coating is provided. As a result, the light incident on the striped copper wiring from the user side is prevented from being specularly reflected, the contrast is improved, and the deterioration of the image quality is suppressed. As a method of providing the black copper oxide film on the copper wiring, Patent Document 1 describes a method of performing blackening treatment on the surface of the copper foil or the copper wiring.

JP 2013-206315 A

  By the way, when the blackening process is performed after the wiring pattern is formed, the surface of the copper wiring is etched. For this reason, the line width and thickness of the copper wiring are reduced until the surface of the copper wiring is blackened. In recent years, with the increase in the area of touch panels and the like, in a fine wiring type transparent electrode, for example, it is required to form an extremely fine copper wiring of 10 μm or less, preferably 6 μm or less. When forming such an extremely fine copper wiring, if the blackening process is performed after the wiring pattern is formed, the copper wiring may be removed by etching before the surface of the copper wiring is blackened. is there. Therefore, with this method, it is difficult to realize an extremely fine copper wiring.

  On the other hand, if a pattern is formed by using a copper foil that has been previously blackened and the surface on the side of the black copper oxide film is placed on the side visible to the user, it is necessary to perform blackening after the wiring pattern is formed. There is no. However, in this case, the following problem occurs. When the blackening treatment is performed on the copper foil, needle-like crystals of copper oxide are formed on the surface of the copper foil. The needle-like crystals produced by the blackening treatment are generally long and brittle, so when another object comes into contact with the surface of the copper foil, the needle-like crystals break and the fine powder of copper oxide is scattered or adhered to the surroundings. The phenomenon called is easy to occur. When this powder-off occurs, the uneven structure on the surface of the copper foil is destroyed, so that there is a possibility that unevenness occurs in the light reflection preventing effect on the surface of the black copper oxide film. In addition, when fine copper oxide powder adheres between copper wirings, there is a risk of problems such as insulation failure.

Furthermore, Patent Document 1 describes that the surface of the black copper oxide film is black. Therefore, it is considered that the main component of the black copper oxide film described in Patent Document 1 is cupric oxide (CuO). However, cupric oxide has higher solubility in acids such as an etchant than cuprous oxide (Cu ₂ O). For this reason, when the wiring pattern is formed by bonding the black copper oxide film side to the PET film, the black copper oxide film is dissolved in the etching solution, and the interface between the copper wiring and the transparent resin substrate is partially peeled off, There is a possibility that the adhesion between the two may be reduced. In order to avoid this, for example, a reduction process may be performed after the blackening process to reduce a part of cupric oxide to cuprous oxide. However, in this case, the lightness of the surface of the black copper oxide film increases depending on the component ratio of cuprous oxide, and it becomes brownish or reddish, so that a sufficient antireflection effect cannot be obtained. There is a fear.

  An object of the present invention is to provide a copper foil for a transparent resin base material and a fine wiring suitable for forming an extremely fine copper wiring having a high scratch resistance and acid solubility resistance and a high antireflection effect on the surface of the transparent resin base material. It is providing the manufacturing method of a transparent resin base material with an attachment and a transparent resin base material with fine wiring.

  Therefore, as a result of intensive studies by the inventors of the present application, the above-described problems have been solved by providing the following fine uneven structure layer on the surface of the copper foil.

  The copper foil for a transparent resin substrate according to the present invention is a copper foil for a transparent resin substrate for forming a copper wiring on the surface of the transparent resin substrate, and cuprous oxide and oxidation are formed on the surface of the copper foil. It is characterized by comprising a fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, which contains cupric composite compound.

  The transparent resin substrate with fine copper wiring according to the present invention is a transparent resin substrate with fine copper wiring in which a copper wiring having a line width of 10 μm or less is provided on the surface of the transparent resin substrate, And a copper foil layer and a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, comprising cuprous oxide and cupric oxide and having a copper composite compound. An uneven structure layer is provided.

  According to this invention, the copper foil for transparent resin base materials contains cuprous oxide and cupric oxide on the surface of copper foil, and the maximum length which consists of these copper complex compounds is a needle shape or plate shape with a maximum of 500 nm or less. A fine concavo-convex structure layer having a fine concavo-convex structure formed by the convex portions. That is, since the fine concavo-convex structure is formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, the needle-like or plate-like projecting longer than 500 nm from the surface of the copper foil. There is no convex part. For this reason, even if other objects come into contact with the surface of the fine concavo-convex structure layer, these needle-like or plate-like convex portions are short and are not easily broken, and have high scratch resistance. Therefore, the copper foil for a transparent resin base material is less likely to be powdered off during handling, etc., can maintain a fine uneven structure on the surface, and fine powder of copper oxide is scattered or adhered to the surroundings. Can be prevented. Therefore, when a fine wiring type transparent electrode such as a touch panel is manufactured using the copper foil for a transparent resin base material, it may be difficult to cause unevenness in the antireflection effect due to powder falling and poor insulation between wirings. it can. For this reason, it becomes easy to provide the said fine uneven structure layer on both surfaces of copper foil.

  Moreover, in this invention, since the said fine concavo-convex structure layer contains cuprous oxide and cupric oxide, compared with the conventional black copper oxide film, according to the ratio containing cuprous oxide, etching liquid It is possible to improve the acid solubility resistance against the like. Therefore, when the fine concavo-convex structure layer side is bonded to the transparent resin base material side and the copper wiring is formed by the etching method, the fine concavo-convex structure layer dissolves and the adhesion between the transparent resin base material and the copper wiring decreases. Can be suppressed.

  Furthermore, since the fine concavo-convex structure is composed of needle-like or plate-like convex portions having a maximum length of 500 nm or less, the maximum pitch between the convex portions tends to be shorter than the wavelength range of visible light. When the maximum pitch is less than or equal to the wavelength range of visible light, the surface reflectance of visible light incident on the fine concavo-convex structure layer can be extremely reduced, and a layer having a high antireflection function can be obtained.

  In the copper foil for a transparent resin substrate according to the present invention, when the fine concavo-convex structure layer is provided on both surfaces of the copper foil, the double-sided black copper foil whose both surfaces are dark brown to black can be obtained. If this is utilized, the fine concavo-convex structure layer provided on one side of the copper foil ensures adhesion to the transparent resin substrate, and the fine concavo-convex structure layer provided on the other side of the copper foil provides copper. Specular reflection of visible light incident on the other surface side of the foil can be suppressed. That is, if the above-mentioned fine wiring type transparent electrode is manufactured using a copper foil having fine concavo-convex structure layers on both sides, the adhesiveness with the transparent resin substrate is good, and the transparent resin substrate side and its side A copper wiring having a layer having a high antireflection function can be formed on either side.

It is a scanning electron microscope observation image which shows the surface of the electrode surface side and deposition surface side of the copper foil for transparent resin base materials (electrolytic copper foil for transparent resin base materials) which concerns on this invention. It is a scanning electron microscope observation image of the cross section of the copper foil for transparent resin base materials (electrolytic copper foil for transparent resin base materials) which concerns on this invention. It is a figure for demonstrating the 1st aspect of the transparent resin base material with fine copper wiring which concerns on this invention. It is a figure for demonstrating the 1st aspect of the transparent resin base material with fine copper wiring which concerns on this invention. It is a figure for demonstrating the 2nd aspect of the transparent resin base material with fine copper wiring which concerns on this invention. It is a figure for demonstrating the 2nd aspect of the transparent resin base material with fine copper wiring which concerns on this invention.

  Hereinafter, the copper foil for transparent resin substrates and the transparent resin substrate with fine copper wiring according to the present invention will be described.

1. First, the copper foil for transparent resin substrates according to the present invention will be described. The copper foil for a transparent resin substrate according to the present invention is a copper foil for a transparent resin substrate for forming a copper wiring on the surface of the transparent resin substrate, and cuprous oxide and oxidation are formed on the surface of the copper foil. It is characterized by comprising a fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, which contains cupric composite compound.

  The said copper foil for transparent resin base materials can be used when manufacturing the fine wiring type transparent electrode of an electrostatic capacitance type touch panel, etc., for example. If the fine concavo-convex structure side is bonded to the transparent resin substrate, the transparent resin substrate and the copper foil can be satisfactorily adhered to each other due to the nano-anchor effect. That is, the fine concavo-convex structure layer can function as an adhesion layer with the transparent resin substrate.

  Further, the surface of the fine concavo-convex structure layer exhibits dark brown to black color due to the extremely fine concavo-convex shape, and the surface reflectance of visible light incident on the fine concavo-convex structure layer can be extremely reduced. That is, if the fine concavo-convex structure layer is disposed on the light incident side, the fine concavo-convex structure layer can function as an antireflection layer. Therefore, when manufacturing a fine wiring type transparent electrode such as a touch panel using the copper foil for the transparent resin substrate, in the final product mode such as a touch panel, the light is incident on the fine wiring type transparent electrode. If the copper wiring is formed so that the fine concavo-convex structure layer is disposed, it is not necessary to perform antireflection treatment on the surface of the copper wiring by blackening treatment after the copper wiring is formed, and the number of processes can be reduced. Further, when the blackening process is performed after the copper wiring is formed, the surface of the copper wiring may be etched in the course of the blackening process, and the wiring width may be narrowed or the copper wiring itself may be removed. However, in the final product mode, if the fine concavo-convex structure layer side is arranged on the light incident side and a copper wiring is formed, the micro-width of the line width of 10 μm or less, preferably 6 μm or less provided with the antireflection layer is provided. Copper wiring can be satisfactorily formed on the transparent resin substrate. Hereinafter, each element will be described.

(1) Transparent resin base material First, a transparent resin base material is demonstrated. The transparent resin base material is, for example, a transparent resin plate base material or film base material having a visible light transmittance of 80% or more, and the visible light transmittance is preferably 85% or more. 90% or more is preferable. The material of the transparent resin base material is not particularly limited as long as the resin base material satisfies the condition, and an appropriate material can be appropriately used depending on the use of the copper foil for the transparent resin base material. For example, when producing a fine wiring type transparent electrode such as a touch panel using the copper foil for a transparent resin substrate according to the present invention, a polyethylene terephthalate resin (PET) substrate having a visible light transmittance of 80% or more, polyethylene A naphthalate resin (PEN) base material, a polyimide resin (PI) base material, etc. can be used suitably.

(2) Copper foil In the present invention, the copper foil is not particularly limited, and may be either an electrolytic copper foil or a rolled copper foil. In the present invention, the thickness of the copper foil is not particularly limited. However, in consideration of forming a copper wiring of 5 μm to 75 μm, which is currently mainstream, on the transparent resin base material, the thickness of the copper foil is preferably 35 μm or less. However, the thinner the copper foil, the easier it is to form an extremely fine wiring pattern with a good etching factor. Therefore, in order to form a wiring pattern having a narrower line width with a favorable etching factor, the thickness of the copper foil is preferably 18 μm or less, and more preferably 12 μm or less. By using a thinner copper foil, for example, an extremely fine wiring pattern having a bottom width of 3 μm can be formed. However, when the thickness of the copper wiring formed on the surface of the transparent resin base material is reduced, the electrical resistance is increased, so that it cannot be applied to a large touch panel or the like. Therefore, from the viewpoint of reducing the electrical resistance, the thickness of the copper foil is preferably 5 μm or more, and more preferably 7 μm or more.

(3) Fine uneven structure layer Next, the fine uneven structure layer will be described. In the present invention, as described above, the fine concavo-convex structure layer includes cuprous oxide and cupric oxide provided on the surface of the copper foil, and a needle-like or plate having a maximum length of 500 nm or less made of these copper composite compounds. It is the fine concavo-convex structure layer which has the fine concavo-convex structure formed of the convex-shaped part.

  In the present invention, even if another object comes into contact with the surface of the fine concavo-convex structure layer by forming the fine concavo-convex structure with a needle-like or plate-like convex part having a maximum length of 500 nm or less, the convex part Because of the short length, damage such as breakage is unlikely to occur. That is, the fine concavo-convex structure layer has a shorter surface convex portion (or needle-like crystal) and higher scratch resistance than a conventional black copper oxide film. No drop occurs, the fine uneven structure on the surface can be maintained, and copper oxide fine powder can be prevented from being scattered or adhered to the surroundings. Therefore, when the fine wiring type transparent electrode or the like is manufactured using the copper foil for the transparent resin base material, unevenness in the antireflection effect due to powder falling can be prevented, resulting in poor insulation between the wirings. Can be difficult.

  Next, the fine concavo-convex structure will be described in more detail with reference to FIGS. 1 and 2. FIG. 1 is a scanning electron microscope observation image showing the surface of a copper foil for a transparent resin substrate provided with fine concavo-convex structure layers on both sides of an electrolytic copper foil as an example of the copper foil for a transparent resin substrate according to the present invention. The surface of the fine concavo-convex structure layer on the electrode surface side and the deposition surface side is shown. More specifically, FIG. 1 shows a planar emission using a field emission type scanning electron microscope at magnifications of 10,000 and 50000 times (inclination angle of 45 ° of the sample at the time of observation with a scanning electron microscope). An example of the surface of the fine uneven structure layer is shown. Moreover, FIG. 2 is a scanning electron microscope observation image which shows the cross section of the copper foil for transparent resin base materials shown in FIG. As shown in FIGS. 1 and 2, countless fine needle-like or plate-like convex portions made of a copper composite compound are observed on the surface of the transparent resin substrate copper foil. It can be confirmed that an extremely fine concavo-convex structure is formed on the surface by densely adhering to each other.

  Here, the convex portion refers to a protruding portion extending in a needle shape or a plate shape from the surface of the copper foil along the surface shape of the copper foil as shown in FIG. 1, and the protruding portion is a copper composite. It is composed of a single crystal of a compound or an aggregate of a plurality of crystals. And, the maximum length of the convex portion is the length of the needle-like or plate-like convex portion when the cross section of the fine concavo-convex structure layer is observed with a field emission type scanning electron microscope. The maximum value is shown. Specifically, as shown in FIG. 2, when the cross section of the transparent resin substrate is observed with the scanning electron microscope, a convex portion extending in a needle shape or a plate shape from the surface of the copper foil in the cross section. Is observed. The maximum value of the length from the base end portion to the tip end portion of the convex portion is referred to. In this invention, it is preferable that the maximum length of the said convex-shaped part is 400 nm or less, and it is more preferable that it is 300 nm or less. As the maximum length of the convex portion becomes shorter, even when another object comes into contact with the surface of the fine concavo-convex structure with a greater force, the convex portion is less likely to be damaged, and the surface shape of the fine concavo-convex structure Is easier to maintain. In addition, the shorter the maximum length, the finer the rugged structure becomes, and due to the surface shape, the function of the fine rugged structure layer as an adhesion layer and the function as an antireflection layer are improved. be able to.

  Moreover, in the copper foil for a transparent resin substrate according to the present invention, when the surface of the fine concavo-convex structure layer is observed in a plane with a tilt angle of 45 ° and a magnification of 50000 times or more using a scanning microscope, Of adjacent convex portions, the length of the tip portion that can be separated and observed from other convex portions is preferably 250 nm or less. Here, “the length of the tip portion that can be observed separately from other convex portions (hereinafter, may be abbreviated as“ the length of the tip portion ”)” refers to the length shown below. . When the surface of the fine concavo-convex structure layer is observed two-dimensionally with a scanning electron microscope, as described with reference to FIG. The interface between the end portion, that is, the convex portion made of the copper composite compound and the copper foil cannot be observed. Therefore, when the surface of the fine concavo-convex structure layer is observed in a planar manner as described above, it is separated from the other bulges among the bulges adjacent to each other while being densely packed, and is independent as one bulge. The portion that can be observed to be present on the surface is called the “tip portion that can be observed separately from other convex portions”, and the length of the tip portion is the tip of the convex portion (that is, the tip portion of the tip portion). The length from the tip) to the position on the most proximal side that can be separated and observed from other convex portions.

  When the length of the tip of the convex portion is 250 nm or less, the maximum length of the convex portion is approximately 500 nm or less, and the function as the adhesion layer of the fine concavo-convex structure layer described above, as the antireflection layer Function can be obtained.

  Furthermore, it is preferable that the length of the tip portion of the convex portion is ½ or less with respect to the maximum length of the convex portion. When the ratio is ½ or less, the nano-anchor effect due to the fine concavo-convex structure can be exhibited while being separated from other convex portions, and adjacent convex shapes at the base end portion of the convex portions. Since the parts are in close contact with each other while being in contact with each other, the copper foil surface can be densely covered with this fine concavo-convex structure.

  Moreover, the average thickness of the fine concavo-convex structure layer is preferably 400 nm or less, and more preferably 350 nm or less. The average thickness of the fine uneven structure layer shown in FIG. 2 is 250 nm. The length and the protruding direction of each convex part forming the fine concavo-convex structure are not constant, and the protruding direction of each convex part is not parallel to the thickness direction of the copper foil. For this reason, the maximum length of the convex portion does not match the maximum thickness of the fine uneven structure layer, and has the relationship of “maximum thickness of the fine uneven structure layer ≦ maximum length of the convex portion”. . When the average thickness of the fine concavo-convex structure layer is 400 nm or less, the maximum length of the convex portion is approximately 500 nm or less. If the average thickness of the fine concavo-convex structure layer is in the range of 100 nm to 400 nm, when the transparent resin base material copper foil is laminated to the transparent resin base material, the transparent resin base material copper foil and the transparent resin base material Good adhesion can be obtained.

  In the fine concavo-convex structure layer, it is impossible to strictly measure the pitch between the convex portions. However, in consideration of the fact that the maximum length of the convex portions is 500 nm or less and the adjacent convex portions at the base end portion of the convex portions are densely in contact with each other, these convex shapes The parts are considered to be adjacent to each other at a pitch shorter than the wavelength range of visible light (780 nm to 380 nm). Since the needle-like or plate-like convex portions having a maximum length of 500 nm or less are arranged at a pitch shorter than the wavelength range of visible light, visible light incident on the fine concavo-convex structure layer is within the fine concavo-convex structure. Attenuates by repeating diffuse reflection. For this reason, the surface reflectance of the fine concavo-convex structure layer is extremely small. As a result, the fine concavo-convex structure layer contains cuprous oxide exhibiting red or reddish brown, but its surface exhibits dark brown to black having a low brightness equal to or higher than that of a black oxide film mainly composed of cupric oxide. . In addition, the component ratio of cuprous oxide and cupric oxide will be described later.

^{CIE-L * a * b *} L * values in the color system of the surface of the fine uneven structure layer (brightness) becomes 30 or less, more preferably 25 or less, more preferably 20 or less. When the L ^* value of the surface of the fine concavo-convex structure layer exceeds 30, the maximum length of the convex portion forming the fine concavo-convex structure layer may be longer than 500 nm. There is a high possibility of not having. This L ^* value can be measured using a spectroscopic color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and a white plate attached to the measuring device can be used for lightness calibration, in accordance with JIS Z8722: 2000. . And the measurement of 3 times is performed regarding the same site | part, and the average value of each measured value can be made into the L ^* value of this invention.

  In the copper foil for a transparent resin substrate according to the present invention, the constituent elements of the fine concavo-convex structure layer are analyzed by X-ray photoelectron spectroscopy (hereinafter referred to as “XPS”). The ratio of the peak area of Cu (I) to the total area of the peak area of Cu (I) and the peak area of Cu (II) obtained in (1) is 50% or more. It is preferable.

  Here, a method for analyzing constituent elements of the fine concavo-convex structure layer by XPS will be described. When the constituent elements of the fine concavo-convex structure layer are analyzed by XPS, each peak of Cu (I) and Cu (II) can be separated and detected. However, when the Cu (I) and Cu (II) peaks are separated and detected, the Cu (0) peak may be observed overlapping the shoulder portion of the large Cu (I) peak. Thus, when the peak of Cu (0) is observed overlappingly, it shall be considered as a Cu (I) peak including this shoulder part. That is, in the present invention, the constituent elements of the copper composite compound that forms the fine concavo-convex structure layer are analyzed using XPS, and Cu (I) and 934 appearing in 932.4 eV corresponding to the binding energy of Cu 2p 3/2, and 934 Each peak obtained by detecting photoelectrons of Cu (II) appearing at .3 eV is separated into waveforms, and the occupied area ratio of the Cu (I) peak is specified from the peak area of each component. However, Quantum 2000 (beam condition: 40 W, 200 um diameter) manufactured by ULVAC-PHI Co., Ltd. is used as an XPS analyzer, and “MultiPack ver. 6.1A” is used as analysis software to perform state / semi-quantitative narrow measurement. be able to.

Here, it is considered that the Cu (I) peak is derived from monovalent copper constituting cupric oxide (Cu ₂ O). And it is thought that a Cu (II) peak originates in the bivalent copper which comprises cuprous oxide (CuO). Furthermore, it is considered that the Cu (0) peak is derived from zero-valent copper constituting metallic copper. Therefore, when the occupied area ratio of the Cu (I) peak is less than 50%, the proportion of cuprous oxide in the copper composite compound constituting the fine concavo-convex structure layer is smaller than the proportion of cupric oxide. it is conceivable that. Here, compared with cupric oxide, cuprous oxide has high solubility with respect to acids, such as etching liquid. Therefore, when the occupied area ratio of the Cu (I) peak is less than 50%, the fine concavo-convex structure layer side of the copper foil for the transparent resin substrate is bonded to the transparent resin substrate, and the copper wiring is formed by the etching method. In this case, the fine concavo-convex structure layer is easily dissolved in the etching solution, and the adhesion between the copper wiring and the transparent resin substrate may be lowered. From this viewpoint, it is preferable that the occupied area ratio of the Cu (I) peak is 70% or more when analyzing the constituent elements of the copper composite compound that forms the fine concavo-convex structure layer by XPS, and it is 80% or more. More preferably, it is particularly preferably 90% or more. As the occupied area ratio of the Cu (I) peak increases, the component ratio of cupric oxide having higher acid solubility with respect to an etching solution or the like becomes higher than that of cuprous oxide. Accordingly, the acid solubility of the fine concavo-convex structure layer with respect to the etching solution is improved, and it becomes possible to reduce the insertion of the etching solution when forming the copper wiring, and the copper wiring having good adhesion to the transparent resin substrate Can be formed. On the other hand, the upper limit value of the occupied area ratio of the Cu (I) peak is not particularly limited, but is 99% or less. The lower the occupied area ratio of the Cu (I) peak, the better the adhesion between the two when the fine uneven structure layer side of the copper foil for transparent resin substrate is bonded to the transparent resin substrate. For this reason, in order to obtain good adhesion between the two, the exclusive area ratio of the Cu (I) peak is preferably 98% or less, and more preferably 95% or less. Note that the occupied area ratio of the Cu (I) peak is calculated by a calculation formula of Cu (I) / {Cu (I) + Cu (II)} × 100 (%).

In the present invention, the specific surface area (hereinafter simply referred to as “specific surface area”) measured by adsorbing krypton on the surface of the fine concavo-convex structure is preferably 0.035 m ² / g or more. . When the specific surface area measured in this manner is 0.035 m ² / g or more, the average thickness of the fine concavo-convex structure layer is 200 nm or more, and copper is applied to the transparent resin substrate via the fine concavo-convex structure layer. Good adhesion can be secured when the foil (copper foil for transparent resin substrate) is laminated. The upper limit value of the specific surface area is not particularly limited, but the fine concavo-convex structure is formed by densely forming needle-like or plate-like convex portions having a maximum length of 500 nm or less. In order to satisfy the shape, the upper limit value of the specific surface area is about 0.3 m ² / g in calculation, and actually about 0.2 m ² / g is the upper limit value. In addition, the specific surface area is measured by using a specific surface area / pore distribution measuring device 3Flex manufactured by Micromeritics Co., Ltd. as a pretreatment by heating the sample at 300 ° C. for 2 hours. The above measurement can be performed by using krypton (Kr).

(4) Manufacturing method of copper foil for transparent resin base materials The copper foil for transparent resin base materials mentioned above can be manufactured as follows, for example. First, an oxidation treatment is performed on the surface of the copper foil, and a fine concavo-convex structure is formed on the copper foil surface by needle-like or plate-like convex portions made of a copper composite compound containing cupric oxide as a main component. Here, the oxidation treatment can be performed, for example, by a wet method in which a treatment solution described later and a copper foil are brought into contact with each other. Next, a reduction treatment for reducing a part of the cupric oxide constituting the fine concavo-convex structure to cuprous oxide is performed, and thereby the surface of the copper foil contains cuprous oxide and cupric oxide, A fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound can be formed.

  Here, as a treatment solution used when oxidizing the surface of the copper foil, for example, an alkaline solution (hereinafter referred to as an alkaline solution) that oxidizes the copper surface and hardly erodes cuprous oxide can be used. . However, when the surface of the copper foil is oxidized with this alkaline solution, cupric oxide needle-like crystals generated on the surface grow longer than 500 nm, making it difficult to form the fine concavo-convex structure layer. That is, in order to form the fine concavo-convex structure layer referred to in the present invention, it is necessary to control so that the acicular crystals of cupric oxide do not grow too much. Therefore, it is preferable to use an alkaline solution containing an oxidation inhibitor capable of suppressing oxidation on the copper foil surface as the treatment solution.

  As said oxidation inhibitor, an amino-type silane coupling agent can be mentioned, for example. If the copper foil surface is oxidized using an alkali solution containing an amino silane coupling agent, the amino silane coupling agent in the alkali solution is adsorbed on the surface of the copper foil, and the copper foil surface by the alkali solution Can be suppressed. As a result, the growth of cupric oxide needle-like crystals can be suppressed, and the fine concavo-convex structure layer having an extremely fine concavo-convex structure on the order of nm can be formed.

  Specific examples of the amino silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- Use of aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. it can. All of these are dissolved in an alkaline solution, stably held in the alkaline solution, and exhibit the effect of suppressing oxidation of the copper foil surface described above.

  As described above, the fine concavo-convex structure formed by subjecting the surface of the copper foil to an oxidation treatment with an alkaline solution containing an amino-based silane coupling agent is substantially maintained even after the reduction treatment. The As a result, it has a fine concavo-convex structure on the order of nm formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, including cuprous oxide and cupric oxide, and having a maximum length of 500 nm or less. An uneven structure layer can be obtained. In the reduction treatment, by adjusting the reducing agent concentration, solution pH, solution temperature, etc., the Cu (I) obtained when analyzing the constituent elements of the copper composite compound forming the fine concavo-convex structure layer described above. The occupied area ratio of the peak of Cu (I) can be appropriately adjusted with respect to the total area of the peak area and the peak area of Cu (II). In addition, when the surface of the copper foil is oxidized with an alkaline solution containing an amino-based silane coupling agent, a trace of the COO-group is confirmed when the constituent elements of the fine concavo-convex structure layer are analyzed by XPS. Therefore, the fine concavo-convex structure layer contains cuprous oxide and cupric oxide, and has a high probability of containing a trace amount of copper carbonate in addition to a trace amount of metal copper.

  As described above, since the oxidation treatment and the reduction treatment can be performed by a wet method using each treatment solution, the fine uneven structure layer is formed on both surfaces of the copper foil by a method such as immersing the copper foil in the treatment solution. It can be formed easily.

2. Next, an embodiment of a transparent resin substrate with fine wiring according to the present invention will be described. In the transparent resin base material with fine wiring according to the present invention, a copper wiring having a line width of 10 μm or less is provided on the surface of the transparent resin base material. The copper wiring includes a copper foil layer, cuprous oxide, A fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, including cupric oxide and comprising these copper composite compounds, To do. The transparent resin substrate with fine wiring can be suitably used as a material for manufacturing a fine wiring type transparent electrode such as a capacitive touch panel. Although various modes can be considered for the transparent resin substrate with fine wiring, here, the first mode shown in FIG. 3 (B) and the second mode shown in FIG. 5 (B) will be mainly described. To do.

(1) 1st aspect First, the transparent resin base material 10 with a fine wiring of a 1st aspect is demonstrated, referring FIG.3 and FIG.4. The transparent resin base material 10 with fine wiring according to the first aspect is obtained by laminating the copper foil 12 for a transparent resin base material provided with the fine uneven structure layer 12b on one side of the copper foil 12a on one side of the transparent resin base material 11. (See FIG. 3 (A)), which is obtained by forming a wiring pattern by an etching method. As shown in FIG. 3 (B), the line width is 10 μm or less on one side 11a of the transparent resin substrate 11. A plurality of copper wirings 13 are provided. In the example shown in FIG. 3B, the copper wiring 13 is in close contact with the transparent resin base material 11 via the fine concavo-convex structure layer 12b provided on one surface of the copper foil layer 12a. These transparent resin base material 11 and fine concavo-convex structure layer 12b have the same configuration as the transparent resin base material and fine concavo-convex structure layer described in the above-described copper foil for transparent resin base material, and copper foil layer 12a It has the same configuration as the copper foil described above. Accordingly, in the first aspect, the description of the same contents as those described above will be omitted, but it should be understood that they have the same functions and effects as described above as long as they have the same configuration as above. .

  In the first aspect, the fine concavo-convex structure layer 12b included in the copper wiring 13 functions as an adhesion layer for closely attaching the transparent resin substrate 11 and the copper foil layer 12a. When the fine concavo-convex structure layer 12b is bonded to the transparent resin base material 11, the needle-like or plate-like convex portions are transparent resin in the process in which the resin material constituting the transparent resin base material 11 is melted and cured by heat. The transparent resin base material 11 and the copper foil layer 12a have good adhesiveness due to the fine uneven structure layer 12b.

  Further, when visible light is incident from the other surface 11 b side of the transparent resin base material 11, the visible light transmitted through the transparent resin base material 11 is a fine uneven structure of the copper wiring 13 provided on the one surface 11 a side of the transparent resin base material 11. The light enters the layer 12b. In this case, since the fine concavo-convex structure layer 12b also functions as an antireflection layer as described above, the reflection of the incident light is suppressed. For example, a transparent optical adhesive film layer (hereinafter referred to as OCA layer) 14 is provided on one side 11 a of the transparent resin substrate 11 so as to cover the exposed portion of the one side 11 a and the copper wiring 13, thereby forming a set of electrode materials 15. (See FIG. 3C). As shown in FIG. 4 (D), two sets of these are prepared, and the other surface 11b side of the transparent resin base material 11 of the other electrode member 15 is in close contact with the surface of the OCA layer 14 of one electrode member 15. By laminating, a fine wiring type transparent electrode such as a touch panel can be obtained. The side on which the fine concavo-convex structure layer 12b of the copper wiring 13 is provided is the viewing side from the user, the cover glass 16 is provided on the surface on the other surface 11b side of the transparent resin substrate 11 of one electrode member 15, and the other By laminating another transparent resin substrate 17 on the surface of the OCA layer 14 of the electrode member 15, a capacitive touch panel can be obtained.

  According to the first aspect, since the fine uneven structure layer 12b is provided on the copper wiring 13 on the side viewed from the user, reflection of light incident on the copper wiring 13 can be prevented, and the display It is possible to prevent a decrease in image quality by preventing a decrease in contrast of the displayed image. Furthermore, since the fine concavo-convex structure layer 12b is provided on the viewing side from the user, it is not necessary to apply blackening treatment again after the wiring pattern is formed. For this reason, it is possible to satisfactorily form a very fine copper wiring having a line width of 10 μm or less, preferably a line width of 6 μm or less.

  Moreover, when the touch panel shown in FIG. 4E is manufactured using the transparent resin base material 10 with fine wiring, the transparent resin base material 11 and the copper wiring 13 are satisfactorily adhered to each other by the fine concavo-convex structure layer 12b. Can do. Here, when the user presses the touch panel, the transparent resin base material 11 bends and a stress is applied between the transparent resin base material 11 and the copper wiring 13. When the operation of the touch panel is repeatedly performed, stress is repeatedly applied between the transparent resin base material 11 and the copper wiring 13. However, in the first aspect, as described above, since the transparent resin base material 11 and the copper wiring 13 are in close contact with each other through the fine concavo-convex structure layer 12b, even if stress is repeatedly applied between the two, the copper wiring 13 can be prevented from peeling from the transparent resin substrate 11.

  Here, in the transparent resin substrate 10 with fine wiring of the first aspect described above, the fine uneven structure layer 12b is provided only on one surface of the copper foil layer 12a. You may provide the fine uneven structure layer 12b on both surfaces. In this case, thereafter, in FIG. 3A, the transparent resin base material copper foil provided with the fine concavo-convex structure layer 12b on both surfaces of the copper foil 12a is bonded to the transparent resin base material 11, and the same as in FIG. If a wiring pattern is formed by an etching method in the same manner as in FIG. 3B after obtaining the laminate, the copper wiring 13 having the fine concavo-convex structure layers 12b on both sides of the copper foil layer 12a can be obtained. If the fine concavo-convex structure layer 12b is provided on both surfaces of the copper foil layer 12a, the fine concavo-convex structure layer 12b is provided not only between the copper wiring 13 and the transparent resin substrate 11, but also between the copper wiring 13 and the OCA layer 14. It can be made to adhere well through. Therefore, even when the touch panel is repeatedly operated, the adhesion between the copper wiring 13 and the transparent resin substrate 11 can be maintained, and the adhesion between the copper wiring 13 and the OCA layer 14 can be maintained.

  Moreover, in the transparent resin base material 10 with the fine copper wiring of the first aspect, since the copper wiring 13 is formed by an etching method, the copper foil layer is exposed on the side surface of the copper wiring 13. Therefore, when a fine wiring type transparent electrode such as a touch panel is manufactured using the transparent resin substrate 10 with fine wiring, the reflected light of the visible light incident on the side surface of the copper foil layer 12a depending on the viewing direction of the user. As a result, the contrast may decrease. Accordingly, the thickness of the copper foil layer 12a is preferably smaller from the viewpoint of suppressing the specular reflection of incident light on the side surface of the copper foil layer 12a, and more preferably 12 μm or less. preferable. The thickness of the copper foil layer 12a is the same as the thickness of the copper foil described above, and the thinner the copper foil layer 12a is also preferable in forming the copper wiring 13 with a favorable etching factor.

(2) Second Aspect Next, a transparent resin substrate 20 with fine wiring according to a second aspect will be described with reference to FIGS. 5 and 6. As shown in FIG. 5A, the transparent resin base material 20 with fine wiring according to the second embodiment is a transparent resin provided with fine concavo-convex structure layers 22b on both sides of a copper foil 22a on both sides of the transparent resin base material 21. After bonding the copper foil 22 for a base material, it was obtained by forming a wiring pattern on both surfaces of the transparent resin base material 21 by an etching method. As shown in FIG. 5 (B), the transparent resin base material 21 A plurality of copper wirings 22 each having a line width of 10 μm or less are provided on both surfaces. Here, the transparent resin base material 21, the copper wiring 23, the copper foil layer 22a, the fine uneven structure layer 22b, and the transparent resin base material copper foil 22 are respectively the copper foil for the transparent resin base material or the first aspect described above. Since the transparent resin base material 11, the copper wiring 13, the copper foil layer 12a, the fine concavo-convex structure layer 12b, and the transparent resin base material copper foil 12 described in the transparent resin base material 10 with fine wiring have the same configuration, Description of duplicate contents is omitted. However, as long as they have the same configuration as described above, they naturally exhibit the same functions and effects.

  In the transparent resin base material 20 with fine wiring of the second aspect, since the copper wiring 23 is provided on both surfaces of the transparent resin base material 21, a fine wiring type transparent electrode can be formed in this state. Next, an OCA layer 24 is provided on each of the two surfaces in the same manner as in the first embodiment (see FIG. 5C), and in the laminated body 25 provided with the OCA layer 24, the side to be viewed from the user side. By providing a cover glass 26 on the surface of the OCA layer 24 and further laminating another transparent resin base material 27 on the surface of the OCA layer 24 on the other surface side, a capacitive touch panel can be obtained.

  In this second aspect, when the fine wiring type transparent electrode is formed by providing the copper wiring 23 on both surfaces of the transparent resin substrate 21, unlike the fine wiring type transparent electrode of the first aspect, the transparent resin base The layer of the material 21 can be further reduced. For this reason, the transmittance | permeability of visible light in the fine wiring type transparent electrode of a 2nd aspect can be made higher than the fine wiring type transparent electrode of a 1st aspect. Moreover, since the number of lamination | stacking of the transparent resin base material 21 decreases compared with the fine wiring type electrode of a 1st aspect, the fine wiring type electrode of a 2nd aspect can reduce a process and cost.

  In the second embodiment, the copper wiring 23 provided with the fine concavo-convex structure layer 22b2 on both surfaces is provided on both surfaces of the transparent resin substrate 21. For this reason, if the said fine wiring type resin base material 20 is used, reflection of the light which injects into the copper wiring 23 can be prevented even if any surface is made into the visual recognition side from a user. Further, no matter which surface is viewed from the user side, since the fine uneven structure layer 22b is provided on the viewing side from the user of the copper wiring 23, it is not necessary to perform blackening after the wiring pattern is formed.

  However, from the viewpoint of preventing reflection of incident light with respect to the copper wiring 23, the copper wiring 23 provided on the surface of the transparent resin base 21 opposite to the viewing side from the user is connected to the transparent resin base 21. The copper wiring 23 provided with the fine uneven structure layer 22b only on the bonding surface is sufficient. However, as described in the first aspect, the copper wiring 23 provided on the surface opposite to the side viewed from the user is provided only with the transparent resin base material 21 by providing the fine uneven structure layer 22b on both surfaces. Instead, the copper wiring having good adhesion to the OCA layer 24 can be obtained.

  Hereinafter, although the Example of the copper foil for transparent resin base materials concerning this invention is demonstrated, the copper foil for transparent resin base materials concerning this invention is not limited to the following Examples, The meaning of this invention is shown. Of course, it can be changed as appropriate without departing from the scope.

In the examples, a copper electrolyte solution having the composition described below is used, DSA is used as the anode, and a cathode (a titanium plate electrode whose surface is polished with No. 2000 polishing paper), the liquid temperature is 50 ° C., and the current density is 60 A / dm ^2. The electrolytic copper foil having a thickness of 18 μm was obtained. And the fine uneven structure layer was formed in both surfaces of the electrolytic copper foil in the following procedures, and it was set as the copper foil for transparent resin base materials which concerns on this invention.

[Copper electrolyte composition]
Copper concentration: 80 g / L
Free sulfuric acid concentration: 140 g / L
Bis (3-sulfopropyl) disulfide concentration: 5 mg / L
Diallyldimethylammonium chloride polymer concentration: 30 mg / L
Chlorine concentration: 25mg / L

Pretreatment: The electrolytic copper foil was immersed in an aqueous sodium hydroxide solution, subjected to alkali degreasing treatment, and washed with water. Then, the electrolytic copper foil after the alkaline degreasing treatment was immersed in a sulfuric acid solution having a hydrogen peroxide concentration of 1 mass% and a sulfuric acid concentration of 5 mass% for 5 minutes, and then washed with water.

Oxidation treatment: The electrolytic copper foil after the above pretreatment was subjected to a liquid temperature of 70 ° C., pH = 12, a concentration of chlorous acid of 150 g / L, and a concentration of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. A predetermined oxidation treatment time (1 minute, 2 minutes, 4 minutes, 10 minutes) is immersed in a sodium hydroxide solution containing 10 g / L, and both surfaces of the electrolytic copper foil are subjected to oxidation treatment. Four types of samples were obtained.

Reduction treatment: Each sample after the oxidation treatment was immersed in an aqueous solution (room temperature) having a dimethylamine borane concentration of 20 g / L adjusted to pH = 12 using sodium carbonate and sodium hydroxide for 1 minute. A fine concavo-convex structure layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound on both surfaces of an electrolytic copper foil after being washed, washed and dried Formed. Table 1 shows the length of the tip portion of the convex portion forming the fine concavo-convex structure together with the maximum length of the convex portion. In addition, the maximum length of the said convex-shaped part and the length of a front-end | tip part are as having mentioned above.

When the state of the surface of the fine concavo-convex structure layer of the copper foil for a transparent resin substrate obtained in this example was analyzed using XPS, “Cu (I)”, “Cu (II)”, and “—COO group” The existence of was confirmed. Further, the occupied area ratio, specific surface area and lightness (L ^* value) of the Cu (I) peak of the copper foil for transparent resin base material obtained in this example are shown in Table 1 below.

Comparative example

  In the comparative example, the same electrolytic copper foil as in the example was used, and after the preliminary treatment was performed in the same manner as in the example, the blackening treatment was performed on both surfaces of the electrolytic copper foil under the following conditions. The copper foil for the material was used.

Blackening treatment: The preliminary solution described above was added to an aqueous solution having a temperature of 85 ° C. containing 10 vol% of “PRO BOND 80A OXIDE SOLUTION” and 20 vol% of “PRO BOND 80A OXIDE SOLUTION”, which are oxidation treatment solutions manufactured by Rohm and Haas Electronic Materials Co., Ltd. The electrolytic copper foil that had been treated was immersed for 5 minutes and subjected to blackening treatment. Table 1 shows the maximum length of the convex portion (needle crystal) and the length of the tip portion formed on the surface of the copper foil by the blackening treatment.

The state of the surface of the blackening treatment layer of the copper foil for a transparent resin substrate obtained in the comparative example was analyzed using XPS. In the blackening treatment layer, the presence of “Cu (I)” and “Cu (II)” was confirmed, but the presence of the “—COO group” was not confirmed. Further, Table 1 shows the occupied area ratio, specific surface area, and lightness (L ^* value) of the Cu (I) peak of the copper foil for transparent resin base material obtained in this comparative example.

  According to this invention, the copper foil for transparent resin base materials contains cuprous oxide and cupric oxide on the surface of copper foil, and the maximum length which consists of these copper complex compounds is a needle shape or plate shape with a maximum of 500 nm or less. A fine concavo-convex structure layer having a fine concavo-convex structure formed by the convex portions. That is, the fine concavo-convex structure is formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less, and there are no needle-like or plate-like convex portions protruding long from the surface of the copper foil. . For this reason, even if other objects come into contact with the surface of the fine concavo-convex structure layer, these needle-like or plate-like convex portions are short, so they are not easily broken and have high scratch resistance. Therefore, the copper foil for a transparent resin base material is less likely to be powdered off during handling, etc., can maintain a fine uneven structure on the surface, and fine powder of copper oxide is scattered or adhered to the surroundings. Can be prevented. Therefore, when a fine wiring type transparent electrode such as a touch panel is manufactured using the copper foil for a transparent resin base material, it may be difficult to cause unevenness in the antireflection effect due to powder falling and poor insulation between wirings. it can. For this reason, it becomes easy to provide the said fine uneven structure layer on both surfaces of copper foil.

  Moreover, in this invention, since the said fine concavo-convex structure layer contains cuprous oxide and cupric oxide, compared with the conventional black copper oxide film, according to the ratio containing cuprous oxide, etching liquid It is possible to improve the acid solubility resistance against the like. Therefore, when the fine concavo-convex structure layer side is bonded to the transparent resin base material side and the copper wiring is formed by the etching method, the fine concavo-convex structure layer dissolves and the adhesion between the transparent resin base material and the copper wiring decreases. Can be suppressed.

  Furthermore, since the fine concavo-convex structure is composed of needle-like or plate-like convex portions having a maximum length of 500 nm or less, the maximum pitch between the convex portions tends to be shorter than the wavelength range of visible light. When the maximum pitch is less than or equal to the wavelength range of visible light, the surface reflectance of visible light incident on the fine concavo-convex structure layer can be extremely reduced, and a layer having a high antireflection function can be obtained.

  Furthermore, in the copper foil for a transparent resin substrate according to the present invention, when the fine concavo-convex structure layer is provided on both sides of the copper foil, both sides can be made a dark brown to black double-sided black copper foil. If this is utilized, the fine concavo-convex structure layer provided on one side of the copper foil ensures adhesion to the transparent resin substrate, and the fine concavo-convex structure layer provided on the other side of the copper foil provides copper. Specular reflection of visible light incident on the other surface side of the foil can be suppressed. That is, if the above-mentioned fine wiring type transparent electrode is manufactured using a copper foil having fine concavo-convex structure layers on both sides, the adhesiveness with the transparent resin substrate is good, and the transparent resin substrate side and its side A copper wiring having a layer having a high antireflection function can be formed on either side.

Claims (10)

A copper foil for a transparent resin base material for forming a copper wiring on the surface of the transparent resin base material,
Fine having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less comprising cuprous oxide and cupric oxide on the surface of the copper foil and made of these copper composite compounds Having an uneven structure layer,
Copper foil for transparent resin base material characterized by this.   With respect to the total area of the peak area of Cu (I) and the peak area of Cu (II) obtained by analyzing the constituent elements of the fine concavo-convex structure layer by X-ray photoelectron spectroscopy, Cu (I) The copper foil for transparent resin base materials of Claim 1 whose ratio which the peak area of occupies is 50% or more. The copper foil for transparent resin base materials of Claim 1 or Claim 2 whose L ^* value in the CIE-L ^* a ^* b ^* color system of the surface of the said fine concavo-convex structure layer is 30 or less.   When the surface of the fine concavo-convex structure layer is observed with a scanning electron microscope at an inclination angle of 45 ° and a magnification of 50000 times or more, it can be separated from other ridges among the ridges adjacent to each other. The length of a suitable front-end | tip part is 250 nm or less, The copper foil for transparent resin base materials as described in any one of Claims 1-3.   The copper foil for transparent resin base materials of Claim 4 whose length of the said front-end | tip part of the said convex-shaped part is 1/2 or less with respect to the said maximum length of the said convex-shaped part.   The copper foil for transparent resin base materials as described in any one of Claims 1-5 provided with the said fine concavo-convex structure layer on both surfaces of the said copper foil. A transparent resin base material with fine copper wiring in which a copper wiring having a line width of 10 μm or less is provided on the surface of the transparent resin base material,
The copper wiring contains a copper foil layer, cuprous oxide and cupric oxide, and a fine unevenness formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of these copper composite compounds. A fine concavo-convex structure layer having a structure,
A transparent resin base material with fine copper wiring.   The said copper wiring is a transparent resin base material with a fine copper wiring of Claim 7 closely_contact | adhered to the surface of the transparent resin base material through the said fine concavo-convex structure layer.   The transparent resin base material with fine copper wiring according to claim 7 or 8, wherein the fine concavo-convex structure layer is provided on a surface of the copper foil layer opposite to a contact surface with the transparent resin base material. .   The resin base material with a fine copper wiring as described in any one of Claims 7-9 in which the cross section of the said copper foil layer is exposed in the side surface of the said copper wiring.

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