JP2006193825A - Perforated electrolytic metal foil, perforated electrolytic metal foil with carrier substrate and their production methods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolytic metal foil with an aperture, in which parameters such as the size, shape, position and depth of fine through-holes and the number of the fine through-holes per unit area, etc, can be designed according to the purpose. <P>SOLUTION: One side of the perforated electrolytic metal foil 1 is determined as a reference plane, and a plurality of fine through-holes 7 that penetrate to the other side are formed almost perpendicularly to the reference plane. Moreover, a carrier substrate and the perforated electrolytic metal foil are bonded together to improve the handleability of the perforated electrolytic metal foil having a plurality of fine through-holes in the thickness direction. In a production method for producing the same, an insulating protrusion is formed on the surface of the carrier substrate, and metal plating is performed on the surface of the carrier substrate on which the insulating protrusion is formed to form the perforated electrolytic metal foil on the surface of the carrier substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a perforated electrolytic metal foil having a plurality of fine through-holes, a perforated electrolytic metal foil with a carrier substrate, and a method for producing them.

  Conventionally, perforated electrolytic metal foil having a plurality of fine through holes has been used in various fields. For example, perforated electrolytic metal foil has applications as a current collector for a fuel cell or a secondary battery or a support for a catalyst that promotes a chemical reaction.

  In particular, in recent years, a demand for a high-capacity secondary battery as a power source for portable electronic devices such as portable PCs and video cameras or a power source for electric vehicles is increasing, and a plurality of fine penetrations are used as a current collector for the secondary battery. A perforated electrolytic metal foil with holes is used.

  In order to meet such market demand, various types of porous electrolytic metal foils having fine through holes formed in the thickness direction of the foil have been proposed (see Patent Documents 1, 2 and 3).

However, the fine through-holes of the porous electrolytic metal foil (perforated electrolytic metal foil) produced by each of the production methods disclosed in these patent documents cannot be controlled in production and are randomly formed (randomly). That is, according to each manufacturing method disclosed in the patent document, parameters such as the size, shape, position, depth, and the number of fine through holes per unit area are arbitrarily controlled intentionally. Can not do it.
Japanese Patent Laid-Open No. 08-236120 JP 50-141540 A Japanese Patent Laid-Open No. 62-240787

  However, in the case of perforated electrolytic metal foil, the size, shape, position, depth, and unit area of the fine through-holes according to the applications accompanying rapid and innovative advances in technology such as nanotechnology. In some cases, it is necessary to form fine through-holes with higher accuracy by changing parameters such as the number of holes for a purpose. Therefore, there has been a demand for provision and provision means of perforated electrolytic metal foil that meets this requirement.

  Therefore, as a result of diligent study, the inventors of the present invention, as a result of perforating electrolytic metal foil, the size, shape, position, depth of the fine through hole, the number of fine through holes per unit area, and the perforated electrolytic metal. In order to provide a perforated electrolytic metal foil in which the type and thickness of the foil can be arbitrarily controlled and a method for producing the perforated electrolytic metal foil, the inventors have conceived the following invention.

Perforated electrolytic metal foil: A perforated electrolytic metal foil according to the present invention is a perforated electrolytic metal foil having a plurality of fine through-holes in the thickness direction, wherein one surface side of the perforated electrolytic metal foil is a reference plane. And a plurality of fine through-holes penetrating on the other surface side of the metal surface so as to be substantially perpendicular to the reference surface.

  And the component which comprises the perforated electrolytic metal foil which concerns on this invention is copper, gold | metal | money, silver, tin, nickel, cobalt, lead, iron, or platinum, or these alloys, or copper, gold | metal | money, silver, tin, It is possible to make it a thing provided with either of the laminated structure which combined either nickel, cobalt, lead, iron, or platinum.

  Moreover, on the electrolytic metal foil which comprises the perforated electrolytic metal foil which concerns on this invention, it is also possible to aim at the improvement of the anticorrosion performance for ensuring long-term preservation | save property as what is equipped with a rust prevention layer.

A perforated electrolytic metal foil with a carrier base material: A perforated electrolytic metal foil with a carrier base material according to the present invention is a carrier for improving the handling property of a perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction. The substrate and the perforated electrolytic metal foil are pasted together.

  And in the perforated electrolytic metal foil with a carrier base material concerning this invention, it is preferable to provide a peeling layer between a perforated electrolytic metal foil and a carrier base material. This release layer will be described later.

  In the perforated electrolytic metal foil with a carrier base material according to the present invention, the carrier base material has a plurality of layers of a first metal layer /.../ nth metal layer (n is an integer of 2 or more). By using a clad metal foil or clad metal plate in a laminated state, a perforated electrolytic metal layer (foil) / first metal layer /.../ n-th metal layer (n is an integer of 2 or more) A plurality of layers may be in a laminated state.

  Further, at least one release layer or the like is provided between any one of the perforated electrolytic metal layer (foil) / first metal layer /... / N-th metal layer (n is an integer of 2 or more). Is also preferable. This release layer will be described later.

Manufacturing method of perforated electrolytic metal foil with carrier base material: The manufacturing method of perforated electrolytic metal foil with a carrier base material according to the present invention includes the following steps a and b.

Step a. A protruding portion forming step of forming insulating protruding portions on the surface of the carrier substrate at a plurality of locations;
Step b. Metal plating is performed on the surface of the carrier base material on which the insulating protrusions are formed, and a metal plating layer is deposited and formed on a region other than the insulating protrusions of the carrier base material. Electrodeposition process to form foil and make a perforated electrolytic metal foil with carrier foil;

  In the method for producing a perforated electrolytic metal foil with a carrier substrate according to the present invention, the carrier substrate used in the step a is any one of the carrier substrate (A) to the carrier substrate (F) shown below. It is preferable to use it.

Carrier substrate (A): Single layer metal foil or metal plate.
Carrier base material (B): A clad metal foil or metal plate in which a plurality of layers of a first metal layer /... / N-th metal layer (n is an integer of 2 or more) are in a laminated state.
Carrier base material (C): any one of the first metal layers of the first metal layer /.../ n-th metal layer (n is an integer of 2 or more) /.../ n-th metal layer A clad metal foil or metal plate comprising at least one release layer in a carrier substrate and a plurality of layers in a laminated state.
Carrier substrate (D): A single layer metal foil or metal plate having a release layer on its surface.
Carrier base material (E): A clad metal foil or metal plate in which a plurality of layers of release layer / first metal layer /... / N-th metal layer (n is an integer of 2 or more) are in a laminated state.
Carrier substrate (F): any of release layer / first metal layer /.../ n-th metal layer (n is an integer of 2 or more) /.../ n-th metal layer A clad metal foil or metal plate comprising at least one carrier base peeling layer between the layers and a plurality of layers in a laminated state.

  In the method for producing a perforated electrolytic metal foil with a carrier substrate according to the present invention, any one of the carrier substrate (A) to the carrier substrate (C) is used as the substrate used in the step a. It is also preferable to provide a release layer forming step between the step a and the step b.

  The release layer used in the method for producing a perforated electrolytic metal foil with a carrier substrate according to the present invention is preferably a metal release layer containing copper, nickel or chromium or an organic release layer containing a triazole compound.

  The insulating protrusion formed in the step a (protrusion forming step) may be formed by any one of an inkjet method, a screen printing method, a gravure printing method, a relief printing method, and an intaglio printing method. preferable.

  Moreover, it is also preferable that the insulating protrusion formed in the step a (projection forming step) is formed using a photosensitive film.

  And said process b. The metal plating in the (deposition step) is preferably a metal plating of copper, gold, silver, tin, nickel, cobalt, lead, iron, platinum, or an alloy plating thereof.

  The step b. The metal plating in the (electrodeposition process) is preferably performed by laminating a plurality of metal plating layers selected from any of copper, gold, silver, tin, nickel, cobalt, lead, iron, and platinum.

Method for producing perforated electrolytic metal foil: The method for producing perforated electrolytic metal foil according to the present invention is characterized by the concept of removing the carrier base material of any of the above-mentioned perforated electrolytic metal foil with a carrier base material. Is.

  In the perforated electrolytic metal foil according to the present invention, the size, position, shape and the like of the fine through-holes can be arbitrarily adjusted. Therefore, the present invention can be applied to any gas, solid, or liquid as a target to be permeated through the fine through-hole, and can be used in any field that is required. Therefore, current collectors such as batteries or catalyst carriers that promote chemical reactions, screen devices for fine powder classification, screen devices for solid-liquid separation processing, nets used for oxygen supply ports of microorganism storage containers, and for clean rooms Dust-proof filters, liquid antibacterial filters, liquid reforming filters for imparting metal ions to liquids and modifying liquids such as drinking water, electromagnetic shielding, clothing materials, magnetic materials, conductive materials, and a wide variety of other It can be used in the field.

  Moreover, even if there exists a request | requirement with respect to a thin perforated electrolytic metal foil of less than 10 micrometers by employ | adopting the structure of a perforated electrolytic metal foil with a carrier base material, it can respond. Due to the presence of the carrier base material supporting the perforated electrolytic metal foil, the handling property of the thin perforated electrolytic metal foil can be easily improved, and the perforated electrolytic metal foil is prevented from being contaminated and scratched in the process.

  Furthermore, the perforated electrolytic metal foil according to the present invention can be easily manufactured by first depositing and peeling off the surface of the carrier substrate, and is a reliable manufacturing method suitable for industrial production. Therefore, high production yield can be secured.

<Perforated electrolytic metal foil>
The form of the perforated electrolytic metal foil according to the present invention will be described. As described above, the perforated electrolytic metal foil according to the present invention is a perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction, and one surface side of the perforated electrolytic metal foil is used as a reference plane. A plurality of fine through holes penetrating on the other surface side of the metal surface are provided so as to be substantially perpendicular to the reference surface. As is clear from the manufacturing method described later, the perforated electrolytic metal foil is directly manufactured by an electrolysis method, and it is ex post facto with respect to a conventional non-porous metal foil. It should be noted that this is distinguished from a metal foil (for example, punching metal) obtained by the hole opening treatment.

  There is no particular limitation on the thickness of the perforated electrolytic metal foil. However, considering that it is manufactured by an electrolytic method, a thickness in the range of 1 μm to 400 μm is common sense. Next, the fine through hole will be described. As will be described later, the fine through hole referred to here forms an insulating projection that becomes an electrodeposition hindrance when forming a metal electrodeposition film, and does not cause electrodeposition on the projection. The location forms a fine through hole. Therefore, the size of the fine through hole depends on the formation accuracy such as the height of the protrusion and the cross-sectional size. Therefore, from the viewpoint of industrial production stability, the diameter of the fine through hole is preferably formed in the range of 1 μm to 300 μm. And according to the use and required quality of the perforated electrolytic metal foil according to the present invention, the size of the fine through hole and the thickness of the foil may be appropriately adjusted. For example, in the case of perforated copper foil, it is a copper foil having a thickness of 3 μm to 35 μm as a market requirement, and the diameter of a fine through hole penetrating from one surface of the copper foil to the other surface is about 10 μm to 200 μm. There is a demand for products that are substantially circular.

  The fine through-holes preferably exist as a plurality of fine through-holes penetrating on the other surface side of the metal surface so that one surface side is a reference surface and is substantially perpendicular to the reference surface. The fine through-hole in such a state is preferable because it has the shortest fine through-hole route and is easy to move ions when used as a negative electrode forming material for a lithium ion secondary battery. On the other hand, for example, described as a concept including a case where the fine through hole extending from the reference surface to the other surface of the electrolytic metal foil is formed obliquely to some extent when viewed from the reference surface, and also to a certain degree of meandering is doing. Further, the cross-sectional shape of the fine through-hole appearing on the surface of the metal foil is not necessarily circular, and can be formed in various shapes such as an elliptical shape, a rectangular shape, a rhombus shape, or a slit shape. However, when the perforated electrolytic metal foil is peeled off from the metal plate carrier, the perforated electrolytic metal foil is easy to peel off, so that the cross-sectional shape of a circle, ellipse, or oval is difficult to break. It is desirable that the cross-sectional shape is surrounded by a smooth curve with no protrusions on the outer edge.

  Furthermore, the arrangement of the fine through-holes in the plane of the foil is determined by considering the application, fine through-hole density (number of fine through-holes in a unit area), regularity or irregularity of the arrangement of the fine through-holes. Is determined. Therefore, the fine through holes may be arranged at a constant pitch interval, or may be a completely random pitch interval. In addition, it is possible to design such that the fine through-hole density is increased or decreased in a certain region of the electrolytic metal foil.

  And the component which comprises the perforated electrolytic metal foil which concerns on this invention is copper, gold | metal | money, silver, tin, nickel, cobalt, lead, iron, or platinum, or these alloys, or copper, gold | metal | money, silver, tin, It is possible to provide any of a laminated structure in which any of nickel, cobalt, lead, iron, or platinum is combined. That is, i) a perforated electrolytic metal foil made of a single metal layer selected from the group consisting of copper, gold, silver, tin, nickel, cobalt, lead, iron and platinum, or ii) copper, gold Two or more kinds of copper-tin alloys selected from the group consisting of silver, tin, nickel, cobalt, lead, iron and platinum, nickel-copper alloys, nickel-cobalt alloys, nickel-iron alloys, gold-platinum alloys, nickel- A perforated electrolytic metal foil made of an alloy layer such as a silver alloy, or iii) two or more layers of two or more components selected from the group consisting of copper, gold, silver, tin, nickel, cobalt, lead, iron and platinum Or a perforated electrolytic metal foil in a clad state.

  Moreover, on the electrolytic metal foil which comprises the perforated electrolytic metal foil which concerns on this invention, it is also possible to aim at the improvement of the anticorrosion performance for ensuring long-term preservation | save property as what is equipped with a rust prevention layer. For this rust prevention, organic rust prevention or inorganic rust prevention can be adopted. For organic rust prevention, it is preferable to use a triazole compound such as benzotriazole or imidazole because it does not cause long-term storage and an electrical failure. On the other hand, in the case of inorganic rust prevention, a metal component exhibiting a sacrificial anticorrosive effect is used as the rust prevention component in consideration of the constituent metal components of the perforated electrolytic metal foil such as zinc for copper.

A perforated electrolytic metal foil with a carrier base material: A perforated electrolytic metal foil with a carrier base material according to the present invention is a carrier for improving the handling property of a perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction. The substrate and the perforated electrolytic metal foil are pasted together. The carrier substrate is present and supports the perforated electrolytic metal foil, so that the perforated electrolytic metal foil has a thickness of less than 10 μm and is easy to bend and wrinkle. Improve. Moreover, the layer of perforated electrolytic metal foil may exist only on one side of the carrier foil or on both sides of the carrier foil.

  The perforated electrolytic metal foil with a carrier base material according to the present invention can be expressed most simply, in order to improve the handling property of the perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction. The open electrolytic metal foil is in a state of being bonded together. In the perforated electrolytic metal foil with a carrier base material, it is also useful to provide a release layer between the perforated electrolytic metal foil and the carrier base material.

  Furthermore, a clad metal foil or a clad metal plate in which a plurality of layers of a first metal layer /.../ nth metal layer (n is an integer of 2 or more) are laminated may be used as the carrier substrate. A carrier group characterized in that a plurality of layers of a perforated electrolytic metal layer (foil) / first metal layer /.../ n-th metal layer (n is an integer of 2 or more) are in a laminated state. It becomes a perforated electrolytic metal foil with a material. Then, at least one release layer or the like is provided between any of the perforated electrolytic metal layer (foil) / first metal layer /.. ./Nth metal layer (n is an integer of 2 or more). Is also possible.

  Here, the carrier base material is in a foil state or a plate state, and functions as a cathode when electrolytically depositing a perforated electrolytic metal foil. In consideration of social conventions, in the present invention, those having a thickness of less than 300 μm are referred to as “foils”, and those having a thickness of 300 μm or more are referred to as “plates”. The material constituting the carrier base material is formed by polarizing the carrier base material itself to the cathode and electrodepositing on the surface at the time of manufacturing the perforated electrolytic metal foil. unnecessary. Therefore, metal materials such as copper, titanium, aluminum, and stainless steel, such as foils and plates, and materials in which the surface of a plastic material is coated with a metal component (for example, a structure having a metal conductive layer on both sides or one side of a plastic film). Etc. can be used. However, a metal material is generally used for the carrier substrate. Regarding this carrier base material, it is preferable to use any of the following carrier base materials (A) to (F).

  The carrier substrate (A) is a single layer metal foil or metal plate. By using the carrier substrate (A), the perforated electrolytic metal foil with a carrier base according to the present invention has a layer configuration of perforated electrolytic metal layer (foil) / metal foil (or metal plate). . And the state which provided the perforated electrolytic metal foil on the surface of this carrier base material (A) is shown in FIG. FIG. 1A schematically shows a state in which a perforated electrolytic metal foil 1 is present on one side of a carrier substrate 2. FIG. 1B schematically shows a state in which the perforated electrolytic metal foil 1 is present on both surfaces of the carrier substrate 2. In the drawing, the insulating protrusion 3 is clearly shown.

  The carrier substrate (B) is a clad metal foil or a metal plate in which a plurality of layers of a first metal layer /.../ n-th metal layer (n is an integer of 2 or more) are in a laminated state. And most simply, it is a clad metal foil or metal plate in a two-layer state in which a first metal layer and a second metal layer are laminated, and this embodiment will be described with reference to the drawings. When the carrier base material (B) is used and the layer structure of perforated electrolytic metal layer (foil) / first metal layer / second metal layer is provided, the clad metal foil or metal plate in such a two-layer state is One of the layers is used for energization during electrolysis as a layer of copper or silver having excellent conductivity, and the other layer is made of nickel, cobalt, or an alloy thereof having high mechanical strength. This is preferable in order to ensure the conductivity and strength of the substrate itself. FIG. 2 shows a state in which a perforated electrolytic metal foil is provided on the surface of the carrier substrate (B). FIG. 2 (a) schematically shows a state in which there is a perforated electrolytic metal foil on one side of the carrier foil. And FIG.2 (b) has shown typically the state which has a perforated electrolytic metal foil on both surfaces of carrier foil. At this time, the first metal layer and the second metal layer may be made of the same material or different metal materials. It should be noted that all the layers from the first metal layer to the nth metal layer are layers having a thickness of at least μm, not a nanometer level composed of a trace element amount.

  The carrier substrate (C) is one of the first metal layer of the first metal layer /.../ nth metal layer (n is an integer of 2 or more) /.../ nth metal layer. It is a clad metal foil or metal plate having at least one carrier substrate peeling layer between layers and having a plurality of layers laminated. And most simply, it is a clad metal foil or a metal plate in a three-layer state of first metal layer / peeling layer in carrier substrate / second metal layer, and this configuration will be described with reference to the drawings. FIG. 3 shows a state in which a carrier base material (C) is used and a perforated electrolytic metal layer (foil) / first metal layer / peeling layer in the carrier base material / second metal layer is provided. . FIG. 3A schematically shows a state in which there is a perforated electrolytic metal foil on one side of the carrier foil. And FIG.3 (b) has shown typically the state which has a perforated electrolytic metal foil in both surfaces of carrier foil. At this time, the first metal layer and the second metal layer may be made of the same material or different metal materials. The carrier base peeling layer is used for peeling between the first metal layer and the second metal layer, and is separated from the carrier base peeling layer so that two carrier bases are separated. A perforated electrolytic metal foil can be obtained. It should be noted that all the layers from the first metal layer to the nth metal layer are layers having a thickness of at least μm, not a nanometer level composed of a trace element amount.

  The carrier substrate (D) is a single layer metal foil or metal plate having a release layer on the surface. By using the carrier base material (D), the perforated electrolytic metal foil with a carrier base material according to the present invention has a layer configuration of perforated electrolytic metal layer (foil) / release layer / metal foil (or metal plate). It will be a thing. That is, a release layer is provided in advance on the surface of the carrier substrate (A), and the release layer is used for peeling off and peeling the carrier substrate and the perforated electrolytic metal foil. FIG. 4 shows a state in which a perforated electrolytic metal foil is provided on the surface of this carrier substrate (C). FIG. 4A schematically shows a state in which there is a perforated electrolytic metal foil on one side of the carrier foil. And FIG.4 (b) has shown typically the state which has a perforated electrolytic metal foil in both surfaces of carrier foil. In the latter case, two perforated electrolytic metal foils can be obtained at a time.

  The carrier substrate (E) is a clad metal foil or metal plate in which a plurality of layers of release layer / first metal layer /... / N-th metal layer (n is an integer of 2 or more) are laminated. . And most simply, it is a clad metal foil or a metal plate in a three-layer state of peeling layer / first metal layer / second metal layer. By using this carrier base material (E), the perforated electrolytic metal foil with a carrier base material according to the present invention is a perforated electrolytic metal layer (foil) / release layer / first metal layer / second metal layer. It will have a configuration. That is, a release layer is provided in advance on the surface of the carrier substrate (B), and the release layer is used for peeling off and peeling the carrier substrate and the perforated electrolytic metal foil.

  The carrier substrate (F) is made of a release layer / first metal layer /.../ n-th metal layer (n is an integer of 2 or more) first metal layer /.../ n-th metal layer. It is a clad metal foil or metal plate in which at least one carrier substrate peeling layer is provided between any of the layers and a plurality of layers are laminated. The simplest is a clad metal foil or metal plate in a four-layer state of release layer / first metal layer / release layer in carrier substrate / second metal layer. By using the carrier base material (F), the perforated electrolytic metal foil with a carrier base material according to the present invention has a perforated electrolytic metal layer (foil) / a release layer / a first metal layer / a release layer in a carrier base material / The layer structure of the second metal layer is provided. That is, a release layer is provided in advance on the surface of the carrier substrate (C), and the release layer is used for peeling off and peeling the carrier substrate and the perforated electrolytic metal foil.

  In the present invention, the term “release layer” is simply the release layer between the carrier substrate and the perforated electrolytic metal foil, and the “release layer in the carrier substrate” is the carrier substrate. It is a release layer that exists inside. Accordingly, in the above and the following, the term “release layer” and “release layer in carrier substrate” are referred to as “release layer and the like”. As the release layer, it is preferable to use either an inorganic release layer or an organic release layer. The release layer and the like are provided so that separation between layers is possible with the release layer and the like as a boundary. In order to use the release layer or the like as the inorganic release layer, it is preferable to use chromium plating, nickel plating, lead plating, chromate treatment, or the like. And in order to use a peeling layer etc. as an organic type peeling layer, what was formed using what consists of 1 type, or 2 or more types selected from a nitrogen-containing organic compound, a sulfur containing organic compound, and carboxylic acid is preferable. .

  More specifically, the components constituting the organic release layer include, among nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Yes. Specifically, examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which are triazole compounds having a substituent, and 1H. It is preferable to use -1,2,4-triazole and 3-amino-1H-1,2,4-triazole.

  As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.

  As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like. The concept relating to the release layer described above can be applied to all release layers referred to in the present invention.

  And in the perforated electrolytic metal foil with a carrier substrate according to the present invention, as in the case of using any of the carrier substrate (D), the carrier substrate (E), or the carrier substrate (F) described above. Assuming that the release layer is located between the perforated electrolytic metal foil and the carrier base material, it is preferable to use the carrier base material and the perforated electrolytic metal foil to separate and peel. This is because the carrier base material can be dissolved and peeled by an etching method, but this leads to an increase in manufacturing cost.

  The carrier base material-attached perforated electrolytic metal foil according to the present invention is a combination of any of the carrier base material and release layer described above and a perforated electrolytic metal foil having a certain laminated structure.

Manufacturing method of perforated electrolytic metal foil with carrier substrate: The manufacturing method of perforated electrolytic metal foil with carrier substrate according to the present invention includes the following steps a and b.

Step a. : This protrusion part formation process is a process of forming an insulating protrusion part in multiple places on the surface of a carrier base material. The carrier substrate is a foil or plate as described above. Insulating protrusions 3 are formed on the surface (one side or both sides) of the carrier substrate 2. FIG. 7A schematically shows a cross section in which the insulating protrusions 3 are formed on the surface of the carrier substrate 2. Moreover, the cross-sectional shape of the insulating protrusion 3 can be applied in various shapes such as a circle, a rectangle, a rhombus, an ellipse, and a slit shape. The insulating protrusion 3 may be slightly tapered from the surface of the carrier substrate 2 upward. This facilitates the peeling of the perforated electrolytic metal foil 1 from the carrier substrate 2.

  At this time, a plurality of means can be adopted as a method of forming the insulating protrusion 3. One of them is a method of forming an insulating protrusion using a printing method. For example, if an insulating protrusion is formed on the surface of the carrier base material by a printing method using a thermosetting resin ink and is cured by heating, the insulating protrusion can be formed. Such a printing method can easily draw the shape of the insulating protrusions and the arrangement of the protrusions freely, has a simple process, and greatly contributes to a reduction in manufacturing cost.

  As the printing method referred to here, any of an inkjet method, a screen printing method, a gravure printing method, a relief printing method, and an intaglio printing method can be used. Formation of the insulating protrusions by these printing methods is performed by a conventional method. Among these, it is preferable to use the ink jet method from the viewpoint of the degree of freedom in design and the ability to cope. In the ink jet method, position information and the like for forming the insulating protrusions of the carrier base material are designed on a computer, and the ink jet printer is controlled by the design information to place the insulating protrusions at a desired position on the carrier base material. I can draw. When the ink jet method is used, the ink thickness per one jet (one jet) when the ink ejected from the ink jet nozzle is formed on the metal plate-like carrier foil 1 is thin. If desired, it is preferable to obtain an insulating protrusion having a desired height by printing the same pattern a plurality of times. In addition, when using the gravure printing method, it should be noted that fine adjustment in accordance with the characteristics of the apparatus is required to stabilize the shape of the formed insulating protrusion.

  Further, another method for forming the insulating protrusion 3 will be described. That is, it is a method using photolithography technology. That is, the insulating protrusion is formed by the following procedure. This will be described below with reference to FIG.

  First, as shown in FIG. 8A, an insulating photosensitive resist layer 4 (hereinafter simply referred to as “resist layer 4”) is formed on the surface of the carrier substrate 2. As the resist layer 4 referred to herein, a photosensitive resist material such as a dry film or a liquid resist used for manufacturing a printed wiring board can be used. In the case of a dry film, it is attached to the surface of the carrier substrate 2 using a laminator. In the case of a liquid resist, the resist layer 3 is preferably formed on the surface of the carrier substrate 2 using a spin coater or the like. In particular, a dry film is a film having a structure in which a resist material is sandwiched between a polyethylene film and a polyester film, and is widely used as an etching resist for printed wiring boards. This dry film can easily have various variations in thickness, and it is easy to widen the thickness width of the perforated electrolytic metal foil, which is the final product.

  Next, as shown in FIG. 8B, in order to form a desired insulating protrusion on the resist layer 4 formed on the surface of the carrier substrate 2, a photomask 5 is formed to form the insulating protrusion. Through the exposure. In general, ultraviolet light (UV light) is used for the exposure (referred to as “UV” in FIG. 8B).

  Then, the exposed resist layer 4 is developed, unnecessary portions of the resist layer 4 are removed, and the insulating protrusions 3 are formed. In this step, an unnecessary portion of the resist layer 3 is removed with an alkaline solution (for example, a sodium carbonate solution having a concentration of about 1% to 5%), and the remaining resist portion forms the shape of the insulating protrusion 3. . The removal method shown in FIG. 8 is a case where a negative type resist is used. When a positive type resist is used by performing a known development process, the resist layer 7 that has been exposed is removed, and the resist layer 3 that has not been exposed remains as a resist mask.

  Before forming the insulating protrusions, the surface of the carrier substrate is pickled with an acid solution such as dilute sulfuric acid or a mixture of dilute sulfuric acid and hydrogen peroxide, and then pure water or ion-exchanged water is used. It is preferable to use after washing with water such as water and drying. This is for ensuring the fixing property of the insulating protrusions to the carrier substrate.

Step b. In this step, as shown in FIG. 7 (b), the carrier base 2 is cathode-polarized on the surface of the carrier base 2 on which the insulating protrusions 3 are formed, and metal plating is performed. A metal plating layer is deposited in a region other than the insulating protrusion 3 of the material 2 to form a perforated electrolytic metal foil 1 on the surface of the carrier base material 2, thereby obtaining a perforated electrolytic metal foil 10 with a carrier foil.

  And in the manufacturing method of perforated electrolytic metal foil with a carrier base material concerning this invention, it is preferable to use any one of the above-mentioned carrier base material (A)-carrier base material (F) as a carrier base material. Here, the description regarding the carrier substrate (A) to the carrier substrate (F) is omitted. The carrier substrate is used so that the metal component constituting the perforated electrolytic metal foil is deposited on the surface using the carrier substrate itself as an electrode (cathode). And, if necessary, use it as an integral part of the perforated electrolytic metal foil until the processing such as bonding the perforated electrolytic metal foil to the base material is completed. It protects against contamination and scratches.

  However, in the method for producing a perforated electrolytic metal foil with a carrier base material according to the present invention, when any one of the carrier base material (A) to the carrier base material (C) is used as the base material used in the step a. It is also preferable to provide a release layer forming step between the step a and the step b. When a release layer forming step is provided at this stage, as shown in FIG. 9 (1) from the state of FIG. 7 (a), the surface of the carrier base material 2 is a portion where there is no insulating protrusion, The same release layer 6 (inorganic or organic release layer) as described above is formed on the surface of the carrier base material on which the plated layer (perforated electrolytic metal foil) is to be formed. At this time, there is no release layer 6 between the insulating protrusion 3 and the carrier substrate 2. However, strictly speaking, except for the case where the inorganic release layer is formed by an electrolytic method, when the organic agent is adsorbed by showering or dipping in order to form the organic release layer, the insulating protrusion 3 The organic agent may be adsorbed on the surface.

  Then, when metal plating is performed on the surface of the carrier base material on which the insulating protrusions 3 are formed, as shown in FIG. 9 (2), a metal is formed in a region other than the insulating protrusions 3 of the carrier base material 2. A plating layer is deposited, and a layer that becomes the perforated electrolytic metal foil 1 is formed on the surface of the carrier base material 2, so that a perforated electrolytic metal foil 10 with a carrier base material is obtained. By providing this release layer 6, the perforated electrolytic metal foil 1 can be peeled off from the carrier substrate 2, and as shown in FIG. An open electrolytic metal foil 1 is obtained.

  Next, a plating method used for forming a layer to be a perforated electrolytic metal foil will be described. As described above, the components of the perforated electrolytic metal foil are copper, gold, silver, tin, nickel, cobalt, lead, iron, or platinum, or an alloy thereof, or copper, gold, silver, tin, nickel, It has one of the laminated structures combining any of cobalt, lead, iron, or platinum, and the bath composition, plating conditions, etc. can be arbitrarily changed as long as the desired plating is possible. No limitation is required. Further, the thickness of the perforated electrolytic metal foil is adjusted by changing the electrodeposition time for electrolytic plating. As an example, the plating solution composition, conditions, etc. which can be used for the plating operation which comprises the perforated electrolytic metal foil which concerns on this invention are illustrated below.

  First, the case where the perforated electrolytic metal foil is composed of a single metal component will be described. When the perforated electrolytic metal foil is made of gold or silver, both a commonly used cyan bath and non-cyan bath can be used. Preferably, a non-cyan bath is used. In the cyanogen bath, when an organic release layer is used as the release layer, the damage is great, and there are increased manufacturing precautions such as forming a thick organic release layer in advance, which tends to complicate process management. It is.

When the perforated electrolytic metal foil is made of copper, a solution used as a copper plating solution can be used. For example, the bath composition has a CuSO ₄ .5H ₂ O concentration of 180 g / L to 240 g / L and a H ₂ SO ₄ concentration of 180 g / L to 210 g / L, a current density of 15 to 30 A / dm ² , and a bath temperature of 30 to 50 For example, the temperature is set as a plating condition. In addition, a potassium pyrophosphate bath or the like is used.

When the perforated electrolytic metal foil is made of tin, a solution used as a tin plating solution can be used. For example, (i) a tin concentration using stannous sulfate is 5 to 30 g / L, a liquid temperature is 20 to 50 ° C., a pH is ^{2 to} 4, and a current density is 0.3 to 10 A / dm ² ; The tin concentration using 1 tin is 20-40 g / L, sulfuric acid concentration 70-150 g / L, liquid temperature 20-35 ° C., cresolsulfonic acid concentration 70-120 g / L, gelatin concentration 1-5 g / L, beta naphthol concentration For example, 0.5 to ² g / L, a current density of 0.3 to 3 A / dm ^{2 and the} like are used as plating conditions.

When the perforated electrolytic metal foil is made of nickel, a solution used as a nickel plating solution can be widely used. For example, (i) nickel sulfate is used, nickel concentration is 5 to 30 g / L, liquid temperature is 20 to 50 ° C., pH is ^{2 to} 4, current density is 0.3 to 10 A / dm ² , and (ii) nickel sulfate is used. Conditions of nickel concentration 5-30 g / L, potassium pyrophosphate concentration 50-500 g / L, liquid temperature 20-50 ° C., pH 8-11, current density 0.3-10 A / dm ² , (iii) nickel sulfate was used It is preferable to set a nickel concentration of 10 to 70 g / L, a boric acid concentration of 20 to 60 g / L, a liquid temperature of 20 to 50 ° C., a pH of ² to 4, and a current density of 1 to 50 A / dm ² as plating conditions. In addition, it is used as plating conditions for other general Watt baths.

In the case of nickel, nickel-phosphorus alloy plating can be obtained by using a phosphoric acid solution. In this case, nickel sulfate concentration 120-180 g / L, nickel chloride concentration 35-55 g / L, H ₃ PO ₄ concentration 30-50 g / L, H ₃ PO ₃ concentration 20-40 g / L, liquid temperature 70-95 ° C., For example, pH of 0.5 to 1.5, current density of 5 to 50 A / dm ² or the like is used as plating conditions.

When the perforated electrolytic metal foil is made of cobalt, a solution used as a cobalt plating solution can be used. For example, (i) using cobalt sulfate, cobalt concentration 5-30 g / L, trisodium citrate concentration 50-500 g / L, liquid temperature 20-50 ° C., pH 2-4, current density 0.3-10 A / dm ² (Ii) using cobalt sulfate, cobalt concentration 5-30 g / L, potassium pyrophosphate concentration 50-500 g / L, liquid temperature 20-50 ° C., pH 8-11, current density 0.3-10 A / dm ² conditions, (iii) cobalt concentration using cobalt sulfate 10~70g / L, boric acid 20 to 60 g / L, liquid temperature 20 to 50 ° C., pH 2 to 4, the current density 1~50A / dm ² plating conditions And so on.

When the perforated electrolytic metal foil is made of lead, a solution used as a lead plating solution can be used. For example, lead borofluoride concentration 250-400 g / L, borofluoric acid concentration 30-50 g / L, boric acid concentration 10-30 g / L, glue concentration 0.1-0.5 g / L, beta naphthol concentration 0.1 ˜1.0 g / L, liquid temperature of 25 to 50 ° C., current density of 1 to 5 A / dm ^{2 and the} like are used as plating conditions.

When the perforated electrolytic metal foil is made of iron, a solution used as an iron plating solution can be used. For example, (i) iron concentration using ferrous sulfate 10-60 g / L, liquid temperature 25-50 ° C., pH 2.5 or less, current density 1-20 A / dm ² , (ii) ferrous sulfate A concentration of 200 to 300 g / L, a ferrous chloride concentration of 35 to 50 g / L, a liquid temperature of 40 to 60 ° C., a pH of 3.5 to 5.5, a current density of 1 to 20 A / dm ^2, etc. are used as plating conditions. .

When the perforated electrolytic metal foil is made of lead, a solution used as a platinum plating solution can be used. For example, using a solution composed of (NH ₄ ) ₂ PtCl having a concentration of 6 to 10 g / L and Na ₂ HPO ₄ · 12H ₂ O having a concentration of 100 to 140 g / L, a liquid temperature of 40 to 70 ° C., a current density of 0.2 to For example, 0.6 A / dm ² or the like is used as a plating condition.

  Next, the case where the perforated electrolytic metal foil is composed of alloy components by alloy plating will be described. Since many alloy compositions can be considered as this alloy plating, only an example is shown below. For example, when the perforated electrolytic metal foil is composed of a silver-palladium alloy, an electroplating bath containing silver cyanide potassium, palladium chloride, potassium acid pyrophosphate, and potassium thiocyanate is used as the silver-palladium alloy plating. A known plating bath and plating conditions may be used.

When the perforated electrolytic metal foil is composed of a nickel-zinc alloy, nickel sulfate is used, nickel concentration is 1 to 2.5 g / L, zinc pyrophosphate is used, zinc concentration is 0.1 to 1 g / L, potassium pyrophosphate Conditions such as a concentration of 50 to 500 g / L, a liquid temperature of 20 to 50 ° C., a pH of 8 to 11, and a current density of 0.3 to 10 A / dm ² are preferable.

When the perforated electrolytic metal foil is composed of a nickel-cobalt alloy, the cobalt sulfate concentration is 80 to 180 g / L, the nickel sulfate concentration is 80 to 120 g / L, the boric acid concentration is 20 to 40 g / L, and the potassium chloride concentration is 10 to 15 g. / L, sodium dihydrogen phosphate concentration of 0.1 to 15 g / L, liquid temperature of 30 to 50 ° C., pH of 3.5 to 4.5, and current density of 1 to 10 A / dm ² are preferable.

When the perforated electrolytic metal foil is composed of a nickel-phosphorus alloy, nickel sulfate 120 to 180 g / l, nickel chloride 35 to 55 g / l, H ₃ PO ₄ 30 to 50 g / l, H ₃ PO ₃ 20 to 40 g / L, liquid temperature of 70 to 95 ° C., pH of 0.5 to 1.5, and current density of 5 to 50 A / dm ² are preferable.

When the perforated electrolytic metal foil is composed of a lead-tin alloy, stannous sulfate 20-40 g / l, lead acetate 15-25 g / l, sodium pyrophosphate 100-200 g / l, EDTA disodium 15-15 25 g / l, PEG-3000 0.8-1.5 g / l, formalin 37% aqueous solution 0.3-1 ml / l, liquid temperature 45-55 ° C., pH 8-10, current density 5-20 A / dm ² Etc. are preferred.

When the perforated electrolytic metal foil is composed of an iron-nickel-cobalt alloy, cobalt sulfate 50 to 300 g / l, nickel sulfate 50 to 300 g / l, ferrous sulfate 50 to 300 g / l, boric acid 30 to 50 g / L, liquid temperature of 45 to 55 ° C., pH of 4 to 5, current density of 1 to 10 A / dm ^{2 and} the like are preferable.

  Furthermore, when the perforated electrolytic metal foil is to be composed of a plurality of metal layers, various metal platings such as copper, gold, silver, tin, nickel, cobalt, lead, iron, or platinum are used. Check in order to form a multi-layer stack. As the plating bath composition and conditions at this time, the plating method for forming the above-described single layer may be adopted in order, and thus description thereof is omitted here.

  The perforated electrolytic metal foil produced as described above is preferably subjected to rust prevention treatment on the outermost surface in order to ensure long-term storage. As the rust-preventing layer, a layer made of a triazole compound such as chromate, zinc, or BTA can be applied. Regarding the formation of the rust-preventing layer, it is possible to use all known methods.

Method for producing perforated electrolytic metal foil: The method for producing perforated electrolytic metal foil according to the present invention is characterized by the concept of removing the carrier base material of any of the above-mentioned perforated electrolytic metal foil with a carrier base material. Is. The carrier base material is used so that the metal component constituting the perforated electrolytic metal foil is deposited on the surface of the carrier base material itself as an electrode (cathode). Therefore, if the carrier base material is removed after the formation of the perforated electrolytic metal foil by the electrolytic method, a perforated electrolytic metal foil is obtained.

  As shown in FIG. 9 (e), the carrier substrate is removed at this time if there is a release layer between the perforated electrolytic metal foil and the carrier base material. Can be separated. At this time, when the insulating protrusion 3 remains in the fine through-hole 7 of the perforated electrolytic metal foil 1, it is preferably removed by swelling with an alkaline solution. On the other hand, as shown in FIG. 7B, when the peeling layer 6 does not exist between the perforated electrolytic metal foil 1 and the carrier substrate 2, the carrier substrate 2 is dissolved and removed by an etching method. Thus, the perforated electrolytic metal foil 1 can be obtained as shown in FIG. In such a case, it is preferable that the entire surface on the perforated electrolytic metal foil 1 side is covered with an etching resist and etching is performed from the carrier base material 2 side. And it is also preferable to employ | adopt the selective etching liquid which melt | dissolves only nickel, without melt | dissolving copper like the case where the perforated electrolytic metal foil 1 is copper and the carrier base material 2 is nickel. In such a case, it is not necessary to coat the entire surface of the perforated electrolytic metal foil with an etching resist.

  In addition, as a method of peeling the perforated electrolytic metal foil 3 from the carrier base material 2, the fine perforated holes of the perforated electrolytic metal foil 1 are immersed in an alkaline solution in the state of the perforated electrolytic metal foil 10 with a carrier base material. It is also possible to make the perforated electrolytic metal foil 1 by swelling and removing the insulating protrusion 3 embedded in the inside 7 and then removing the carrier base material 2.

  Moreover, after the perforated electrolytic metal foil is peeled off from the carrier base material, a rust preventive treatment is performed on both sides of the perforated electrolytic metal foil to obtain more reliable oxidation resistance. And long-term storage can be ensured. In the drawings, the description of the antirust treatment layer is omitted.

  In this example, a single layer metal foil (35 μm thick copper foil) was pickled with dilute sulfuric acid as the carrier substrate (A), then washed with water, dried and cleaned. Next, a dry film having a thickness of 20 μm was attached to the glossy surface of the copper foil after pickling with a laminator to form a resist film.

  Next, a photomask is arranged on the resist film, and exposure and development are performed so that a circular pattern having a diameter of 25 μm and a pattern in a grid pattern can be formed so that the distance between the centers of the circular shapes is 50 μm. Insulating protrusions were formed.

  Then, an aqueous solution containing carboxybenzotriazole at a concentration of 5 g / 1 was showered on the exposed portion of the carrier base material (copper foil) on which the insulating protrusions were formed to form a release layer. . As described above, the precipitation surface (hereinafter simply referred to as “deposition surface”) of the perforated electrolytic metal foil of the carrier substrate was formed.

  When the formation of the precipitation surface was completed, a 10 μm-thick perforated electrolytic metal foil was formed by precipitation using the 12 types of electrolytic solutions and plating conditions listed in Table 1. Note that an insoluble electrode (DSE) was used as the anode electrode, and a DC power source was used as the power source (the same applies hereinafter).

  When a metal component is electrodeposited on the deposition surface as described above, a perforated electrolytic metal foil with a carrier substrate is obtained. Then, no copper electrodeposition occurs at the position where the insulating protrusions exist, and the electrodeposited copper film has a carrier substrate in which a perforated electrolytic metal foil having fine through-holes with a diameter of 20 μm and a carrier substrate are bonded together. It became a perforated electrolytic metal foil with a material.

  Therefore, the perforated electrolytic metal foil with a carrier substrate is immersed in a 3% aqueous sodium hydroxide solution to swell the resist component of the insulating protrusions remaining in the fine through holes of the perforated electrolytic metal foil. And the perforated electrolytic metal foil was peeled off. As a result, a perforated electrolytic metal foil 1 having fine through holes 7 as shown in the enlarged schematic diagram of FIG. 10 was obtained.

  Furthermore, the perforated electrolytic metal foil (perforated electrolytic copper foil) 1 obtained as described above is immersed in a 1 g / L benzotriazole aqueous solution for 10 seconds and pulled up to perform organic rust prevention treatment on both sides. did. This rust prevention treatment was performed only when the perforated electrolytic metal foil was formed under the conditions of Condition 1, Condition 8, Condition 9, and Condition 12.

  The typical observation photograph of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained by this Example (Condition 1) is shown. That is, an SEM observation image at a magnification of 500 times is shown in FIG. 11, and an SEM observation image at a magnification of 3000 times of fine through holes of the perforated electrolytic metal foil (perforated electrolytic copper foil) is shown in FIG. This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. The perforated electrolytic metal foil was placed on a rubber mat for convenience of photography. Therefore, the SEM photographic image of the rubber mat under the perforated electrolytic metal foil that looks like burrs and scales is completely unrelated to the present invention, and beautiful fine through holes are formed in the foil. Can understand.

  In this embodiment, a clad metal foil in which a plurality of layers of a first metal layer /... ./N-th metal layer (n is an integer of 2 or more) is laminated is used as the carrier substrate (B). It was. More specifically, the clad metal foil used here was obtained by providing a cobalt layer having a thickness of 10 μm by electrolysis on the surface of a rolled nickel foil having a thickness of 20 μm. This clad foil was pickled in the same manner as in Example 1, and a dry film having a thickness of about 25 μm was attached by a laminator to form a resist film. Then, 12 kinds of perforated electrolytic metal foils with a thickness of 20 μm were formed under various electrolytic solutions and plating conditions listed in Table 1 in the same manner as in Example 1 in the case where the conditions 1 to 12 were applied. Precipitation was formed.

  As described above, when a metal component is electrodeposited on the deposition surface, a carrier in which a perforated electrolytic metal foil having fine through-holes with a diameter of 20 μm and a carrier base material are bonded together as in the case of Example 1. A perforated electrolytic metal foil with a base material was obtained, and the carrier base material was removed from the perforated electrolytic metal foil with a carrier base material to obtain a perforated electrolytic metal foil. In addition, the antirust process with respect to the obtained perforated electrolytic metal foil was performed only when the perforated electrolytic metal foil was formed on condition 1, condition 8, condition 9, and condition 12.

  Representative observation photographs of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained in this example are the SEM observation image (FIG. 11) at a magnification of 500 times and the SEM observation image (FIG. 12) at a magnification of 3000 times. ) Is omitted because it is the same as). This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. As a result of observation, as in Example 1, it was confirmed that beautiful fine through holes were formed in the perforated electrolytic metal foil.

  In this embodiment, as the carrier substrate (C), the first metal layer of the first metal layer /... / Nth metal layer (n is an integer of 2 or more) /. A clad metal foil having at least one carrier base peeling layer between any one of the metal layers and having a plurality of laminated layers was used. More specifically, the clad metal foil used here is showered with an aqueous solution containing carboxybenzotriazole at a concentration of 5 g / 1 on one side of a 10 μm-thick rolled nickel foil to form a release layer in the carrier substrate. Then, on the release layer in the carrier substrate, a nickel layer having a thickness of 10 μm was used under the condition 5 nickel electrolyte and plating conditions. This clad foil was pickled in the same manner as in Example 1, and a dry film having a thickness of about 25 μm was attached to both sides of the clad foil with a laminator to form a resist film. Then, similarly to the case of Example 1, insulating protrusions are provided on both sides of the clad foil, and a release layer is formed between the perforated electrolytic metal foil and the carrier substrate. In the same manner as in Example 1, 12 types of perforated electrolytic metal foils having a thickness of 20 μm were deposited on both surfaces of the clad foil on the carrier base material under various electrolytic solutions and plating conditions listed in Table 1.

  As described above, when a metal component is electrodeposited on the deposition surface, a perforated electrolytic metal with a carrier base material, in which a perforated electrolytic metal foil having fine through-holes with a diameter of 20 μm is bonded to both surfaces of the carrier base material. It becomes a foil. Then, by separating from the release layer in the carrier base material between the nickel layer and the nickel layer, two perforated electrolytic metal foil / peeling layers (however, between the insulating protrusion and the carrier base material) There was no release layer) / nickel layer (functioning as a carrier substrate). In this example, this is called a perforated electrolytic metal foil with a carrier substrate.

  And the carrier base material was removed from this perforated electrolytic metal foil with a carrier base material to obtain a perforated electrolytic metal foil. In addition, the antirust process with respect to the obtained perforated electrolytic metal foil was performed only when the perforated electrolytic metal foil was formed on condition 1, condition 8, condition 9, and condition 12.

  Representative observation photographs of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained in this example are the SEM observation image (FIG. 11) at a magnification of 500 times and the SEM observation image (FIG. 12) at a magnification of 3000 times. ) Is omitted because it is the same as). This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. As a result of observation, as in Example 1, it was confirmed that beautiful fine through holes were formed in the perforated electrolytic metal foil.

  In this example, as the carrier substrate (D), a single layer metal foil (35 μm thick copper foil) used in Example 1 with a release layer formed in advance was used. Therefore, the release layer is also present between the carrier substrate and the insulating protrusion. And when using this carrier base material (D), the post-formation of the pickling process and peeling layer which were used in Example 1 was abbreviate | omitted. That is, a dry film having a thickness of 20 μm was pasted on the release layer with a laminator to form a resist film. Hereinafter, in the same manner as in Example 1, insulating protrusions were formed, and this surface was used as a deposition surface of the perforated electrolytic metal foil (hereinafter simply referred to as “deposition surface”).

  Then, when the formation of the deposition surface was completed, a 10 μm-thick perforated electrolytic metal foil was deposited and formed using the 12 types of electrolytic solutions and plating conditions listed in Table 1. Thereafter, in the same manner as in Example 1, a perforated electrolytic metal foil with a carrier substrate was obtained, and further a perforated electrolytic metal foil was obtained.

  Representative observation photographs of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained in this example are the SEM observation image (FIG. 11) at a magnification of 500 times and the SEM observation image (FIG. 12) at a magnification of 3000 times. ) Is omitted because it is the same as). This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. As a result of observation, as in Example 1, it was confirmed that beautiful fine through holes were formed in the perforated electrolytic metal foil.

  In this example, as the carrier base material (E), a cobalt layer having a thickness of 10 μm is provided by electrolysis on the surface of the rolled nickel foil having a thickness of 20 μm used in Example 2, and is peeled in advance on the cobalt layer. What formed the layer was used. Therefore, the release layer is also present between the carrier substrate and the insulating protrusion. And when using this carrier base material (E), the post-formation of the pickling process and peeling layer which were used in Example 1 was abbreviate | omitted. That is, a 25 μm-thick dry film was pasted on the release layer with a laminator to form a resist film. Hereinafter, in the same manner as in Example 2, insulating protrusions were formed, and this surface was used as a deposition surface of the perforated electrolytic metal foil (hereinafter simply referred to as “deposition surface”).

  Then, when the formation of the deposition surface was completed, a 10 μm-thick perforated electrolytic metal foil was deposited and formed using the 12 types of electrolytic solutions and plating conditions listed in Table 1. Thereafter, in the same manner as in Example 2, a perforated electrolytic metal foil with a carrier substrate was obtained, and further a perforated electrolytic metal foil was obtained.

  Representative observation photographs of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained in this example are the SEM observation image (FIG. 11) at a magnification of 500 times and the SEM observation image (FIG. 12) at a magnification of 3000 times. ) Is omitted because it is the same as). This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. As a result of observation, as in Example 1, it was confirmed that beautiful fine through holes were formed in the perforated electrolytic metal foil.

  In this example, as the carrier base material (F), an aqueous solution containing carboxybenzotriazole at a concentration of 5 g / 1 is showered on one side of the 10 μm-thick rolled nickel foil used in Example 3 to form the carrier base material. An inner release layer was formed, and a 10 μm thick nickel layer was provided on the carrier substrate inner release layer under the condition 5 nickel electrolyte and plating conditions, and the release layer was formed on both sides in advance. A thing was used. Therefore, the release layer is also present between the carrier substrate and the insulating protrusion. And when using this carrier base material (F), the post-formation of the pickling process and peeling layer which were used in Example 1 was abbreviate | omitted. That is, a 25 μm-thick dry film was pasted on the release layers on both sides with a laminator to form a resist film. Hereinafter, in the same manner as in Example 3, insulating projections were formed on both surfaces, and both surfaces were used as the deposition surface of the perforated electrolytic metal foil (hereinafter simply referred to as “deposition surface”).

  Then, when the formation of the deposition surface was completed, a 10 μm-thick perforated electrolytic metal foil was deposited on both surfaces under the 12 types of electrolytic solutions and plating conditions listed in Table 1. Thereafter, in the same manner as in Example 3, a perforated electrolytic metal foil with a carrier substrate was obtained, and further a perforated electrolytic metal foil was obtained.

  Representative observation photographs of the perforated electrolytic metal foil (perforated electrolytic copper foil) obtained in this example are the SEM observation image (FIG. 11) at a magnification of 500 times and the SEM observation image (FIG. 12) at a magnification of 3000 times. ) Is omitted because it is the same as). This observation result is the same even if the manufacturing conditions of the perforated electrolytic metal foil shown in Table 1 are changed. As a result of observation, as in Example 1, it was confirmed that beautiful fine through holes were formed in the perforated electrolytic metal foil.

  In the perforated electrolytic metal foil according to the present invention, fine through-holes can be formed in any shape according to the design and any number per unit area. Therefore, it can be used in various wide applications. For example, current collectors such as batteries or catalyst carriers that promote chemical reactions, screen devices for ultrafine powder, dustproof / gas filters for clean rooms (especially conductive perforated metal foils are collected by static electricity). Dust), filters for water purifiers (especially in the case of ferromagnetic perforated electrolytic metal foil, it is possible to produce drinking water through a filter with magnetic force applied to the metal foil), antibacterial filters, electromagnetic shields ( In particular, conductive perforated metal foil), vent hole nets for microorganism storage boxes, anti-static mats with perforated metal foil placed inside or under the mat and connected to the ground, water repellent and breathable It is applicable to a wide range of industrial application fields, such as a cloth in which a perforated metal foil is sandwiched between cloths such as Teflon (registered trademark) materials.

  The perforated electrolytic metal foil according to the present invention can be provided to the market in the form of a perforated electrolytic metal foil with a carrier substrate, and the perforated electrolytic metal foil is good even when the thickness of the perforated electrolytic metal foil is less than 10 μm. Handling properties can be ensured, and work efficiency can be greatly improved. Moreover, depending on the application, it can be used in a product as it is in the state of a perforated electrolytic metal foil with a carrier substrate.

  Furthermore, the manufacturing method of the perforated electrolytic metal foil and the perforated electrolytic metal foil with a carrier base material according to the present invention is based on the manufacturing method of the perforated electrolytic metal foil with a carrier base material, and the carrier base material is removed therefrom. Thus, a perforated electrolytic metal foil can be easily obtained.

It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier base material according to the present invention (when the carrier base material (A) is used). It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier base material according to the present invention (when the carrier base material (B) is used). It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier base material according to the present invention (when the carrier base material (C) is used). It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier substrate according to the present invention (when the carrier substrate (D) is used). It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier base material according to the present invention (when the carrier base material (E) is used). It is a cross-sectional schematic diagram of the perforated electrolytic metal foil with a carrier base material according to the present invention (when the carrier base material (F) is used). It is the figure which showed typically the procedure until it forms an insulating protrusion part in the surface of a carrier base material, and obtains a perforated electrolytic metal foil. It is a figure for demonstrating notionally the process of forming an insulating protrusion part in the surface of a carrier base material (resist method). It is the figure which showed typically the procedure until it forms an insulating protrusion part in the surface of a carrier base material, and obtains a perforated electrolytic metal foil. In order to understand arrangement | positioning of the fine through-hole of the perforated electrolytic metal foil which concerns on this invention, it is a conceptual schematic diagram at the time of seeing planarly. It is a photograph (500-times multiplication factor) of the scanning microscope observation image of the apertured electrolysis metal foil manufactured by the Example which concerns on this invention. It is a photograph (300-times multiplication factor) of the scanning microscope observation image of the several fine through-hole arrange | positioned at the perforated electrolytic metal foil manufactured by the Example which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Perforated electrolytic metal foil 2 Carrier base material 3 Insulating protrusion 4 Resist layer 5 Photomask 6 Peeling layer 7 Fine through-hole 10 Perforated electrolytic metal foil with carrier base material 11 First metal layer 12 Second metal layer 20 Carrier Release layer in substrate

Claims (16)

A perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction,
A hole comprising a plurality of fine through-holes penetrating on the other surface side of the metal surface so that one surface side of the perforated electrolytic metal foil is a reference surface and substantially perpendicular to the reference surface Open electrolytic metal foil. The metal of the perforated electrolytic metal foil is copper, gold, silver, tin, nickel, cobalt, lead, iron, platinum, or an alloy thereof, or gold, silver, tin, nickel, cobalt, lead, iron, or 2. The perforated electrolytic metal foil according to claim 1, comprising any one of a laminated structure in which any one of platinum is combined. The perforated electrolytic metal foil according to claim 1 or 2, wherein a rust prevention layer is formed on the perforated electrolytic metal foil. With carrier base material, wherein the carrier base material and the perforated electrolytic metal foil are in a state of being bonded together in order to improve the handling property of the perforated electrolytic metal foil having a plurality of fine through holes in the thickness direction Perforated electrolytic metal foil. The perforated electrolytic metal foil with a carrier base material according to claim 4, wherein a release layer is provided between the perforated electrolytic metal foil and the carrier base material in the perforated electrolytic metal foil with a carrier base material. By using a clad metal foil or a clad metal plate in which a plurality of layers of a first metal layer /.../ nth metal layer (n is an integer of 2 or more) are laminated as the carrier substrate,
5. A plurality of layers of perforated electrolytic metal layer (foil) / first metal layer /.../ nth metal layer (n is an integer of 2 or more) are in a laminated state. Perforated electrolytic metal foil with carrier substrate. 7. At least one release layer or the like is provided between any of the perforated electrolytic metal layer (foil) / first metal layer... / N-th metal layer (n is an integer of 2 or more). A perforated electrolytic metal foil with a carrier base material as described in 1. A method for producing a perforated electrolytic metal foil with a carrier base material according to any one of claims 4 to 7,
A method for producing a perforated electrolytic metal foil with a carrier substrate, comprising the following steps a and b.
Step a. A protruding portion forming step of forming insulating protruding portions on the surface of the carrier substrate at a plurality of locations;
Step b. Metal plating is performed on the surface of the carrier base material on which the insulating protrusions are formed, and a metal plating layer is deposited and formed on a region other than the insulating protrusions of the carrier base material. Electrodeposition process of forming a foil and forming a perforated electrolytic metal foil with a carrier substrate; The method for producing a perforated electrolytic metal foil with a carrier base material according to claim 8, wherein the carrier base material used in the step a is any one of the following carrier base material (A) to carrier base material (F).
Carrier substrate (A): Single layer metal foil or metal plate.
Carrier base material (B): A clad metal foil or metal plate in which a plurality of layers of a first metal layer /... / N-th metal layer (n is an integer of 2 or more) are in a laminated state.
Carrier base material (C): any one of the first metal layers of the first metal layer /.../ n-th metal layer (n is an integer of 2 or more) /.../ n-th metal layer A clad metal foil or metal plate comprising at least one release layer in a carrier substrate and a plurality of layers in a laminated state.
Carrier substrate (D): A single layer metal foil or metal plate having a release layer on its surface.
Carrier base material (E): A clad metal foil or metal plate in which a plurality of layers of release layer / first metal layer /... / N-th metal layer (n is an integer of 2 or more) are in a laminated state.
Carrier substrate (F): any of release layer / first metal layer /.../ n-th metal layer (n is an integer of 2 or more) /.../ n-th metal layer A clad metal foil or metal plate comprising at least one carrier base peeling layer between the layers and a plurality of layers in a laminated state. A case where any one of the carrier base material (A) to the carrier base material (C) is used as the base material used in the step a, and a release layer forming step is provided between the step a and the step b. Item 10. A method for producing a perforated electrolytic metal foil with a carrier substrate according to Item 8 or Item 9. The method for producing a perforated electrolytic metal foil with a carrier substrate according to claim 9 or 10, wherein the release layer is a metal release layer containing copper, nickel, or chromium or an organic release layer containing a triazole compound. The insulating protrusion formed in the step a is formed by any one of an ink jet method, a screen printing method, a gravure printing method, a relief printing method, and an intaglio printing method. A method for producing a perforated electrolytic metal foil with a carrier substrate as described in 1. The method for producing a perforated electrolytic metal foil with a carrier substrate according to any one of claims 8 to 11, wherein the insulating protrusion formed in the step a is formed using a photosensitive film. Step b. The metal plating in (Electrodeposition process) is any one of copper, gold, silver, tin, nickel, cobalt, lead, iron, platinum, or alloy plating thereof. A method for producing a perforated electrolytic metal foil with a carrier substrate according to any one of the above. Step b. The metal plating in (Electrodeposition process) is any one of claims 8 to 13, wherein a plurality of metal plating layers selected from copper, gold, silver, tin, nickel, cobalt, lead, iron, and platinum are laminated. A method for producing a perforated electrolytic metal foil with a carrier substrate as described in 1. A method for producing a perforated electrolytic metal foil according to any one of claims 1 to 3,
A method for producing a perforated electrolytic metal foil, wherein the carrier base material of the perforated electrolytic metal foil with a carrier base according to any one of claims 8 to 15 is removed.