JP5640396B2 - Metal foil obtained by a method for producing a patterned metal foil - Google Patents

Description

  The present invention relates to a metal foil obtained by a method for producing a patterned metal foil (hereinafter referred to as a patterned metal foil).

  For example, conventionally, when obtaining an electric double layer capacitor having an excellent charge / discharge cycle, high withstand voltage, and large capacity, it is necessary to store lithium ions in the positive electrode and the negative electrode in advance (Patent Document 1). As a means for storing lithium in the current collector, it is advantageous to use a current collector with a hole (Patent Document 2). Here, specific examples of the perforated current collector include expanded metal, punching metal, net, foam, and perforation by photolithography. However, these current collectors have a problem in mass productivity, and it has been difficult to reduce the cost in terms of cost.

Japanese Patent No. 3689948 Japanese Patent No. 3485935

In the above-described current collector manufacturing method, there is a problem in mass productivity, and it is difficult to reduce the cost. For example, in the method of punching holes in a current collector, when a hole having a diameter of 30 μm or less is formed by punching, the punching mold can be used repeatedly several tens to several hundreds of times. There is a problem that it cannot be used repeatedly and thousands of times and cannot be mass-produced. In addition, when the hole forming process for the current collector is performed by a photolithography method, complicated processes such as a resist pattern forming process and an etching process are required one by one in the manufacture of the product.
The metal foil provided with the hole pattern and other patterns may have various aspects and uses other than the current collector with a hole, but the production of the metal foil has the same problems as described above.

  In view of these problems, the present invention provides a method for producing a patterned metal foil with high productivity.

The present invention relates to the following.
1. (A) An electroconductive substrate for plating in which an insulating layer is formed on the surface of the electroconductive substrate, and a concave portion is formed in the insulating layer that is wide toward the opening direction and exposes the electroconductive substrate. (B) A metal foil obtained by a method for producing a patterned metal foil, comprising a step of depositing a metal on the surface of the substrate by plating, and (b) a step of peeling the metal deposited on the surface of the conductive substrate.
2. The metal foil obtained by the manufacturing method of the patterned metal foil of claim | item 1 currently formed so that an insulating layer may draw a geometric figure in a conductive base material for plating, or it may draw a geometric figure itself.
3. Item 3. The metal foil obtained by the method for producing a patterned metal foil according to Item 1 or 2, wherein the insulating layer of the conductive base material for plating is made of diamond-like carbon (DLC) or an inorganic material.
4). Insulating layer for plating conductive substrate, DLC, Al ₂ O ₃ or a metal foil obtained by the production method of the patterned metal foil according to any one of claim 1 to 3, a SiO _2.
5. Item 5. The metal foil obtained by the method for producing a patterned metal foil according to any one of Items 1 to 4, wherein the insulating layer of the conductive substrate for plating is made of DLC having a hardness of 10 to 40 GPa.
6). In the conductive substrate for plating, the insulating layer has a convex shape with an area of the bottom of 1 to 1 × 10 ⁶ square microns, and the convex shape is distributed at intervals of 1 to 1000 μm. Metal foil obtained by the manufacturing method of the patterned metal foil in any one of 5.
7). The metal foil obtained by the manufacturing method of the patterned metal foil in any one of claim | item 1 -6 whose angle of a recessed part side surface is 30 degree | times or more and less than 90 degree | times in the electroconductive base material for plating.
8). The metal foil obtained by the manufacturing method of the patterned metal foil in any one of claim | item 1 -7 whose angle of a recessed part side surface is 30 degree | times or more and 60 degrees or less on the insulating layer side in the electroconductive base material for plating.
9. The metal foil obtained by the manufacturing method of the patterned metal foil in any one of claim | item 1 -8 whose thickness of an insulating layer is 0.1-100 micrometers in the electroconductive base material for plating.
10. Items 1 to 1 in which an intermediate layer containing any one or more of Ti, Cr, W, Si or nitrides or carbides thereof is interposed between the conductive substrate and the insulating layer in the conductive substrate for plating. Metal foil obtained by the manufacturing method of the patterned metal foil in any one of 9.
11. Item 11. A metal foil obtained by the method for producing a patterned metal foil according to any one of Items 1 to 10, wherein the surface of the conductive substrate is made of steel or Ti in the conductive substrate for plating.
12 Item 12. The metal foil obtained by the method for producing a patterned metal foil according to any one of Items 1 to 11, wherein the conductive substrate for plating is wound around a conductive roll (drum) or a roll.

  According to the method for producing a patterned metal foil of the present invention, in the conductive base material for plating, since the concave portion in which the metal layer is formed by plating is wide toward the opening direction, Since the insulating layer formed on the surface of the conductive base material has a convex shape that spreads out, the patterned metal foil obtained by plating can be easily peeled. In addition, since the insulating layer of the conductive base material for plating is made of DLC or an inorganic material, the adhesion to the conductive base material is excellent, and its peeling resistance is excellent. In the manufacturing method of the patterned metal foil of the present invention, it is repeated. The use of is excellent. Therefore, according to the metal foil obtained by the production method of the present invention, the patterned metal foil can be produced efficiently and with good productivity. Said insulating layer can improve adhesiveness with an electroconductive base material by an intermediate | middle layer, Thereby, the lifetime of the electroconductive base material for plating can further be lengthened. Thereby, the metal foil of the same quality can be provided at a low price.

The perspective view which shows an example of the electroconductive base material for plating of this invention. AA sectional drawing of FIG. Sectional drawing which shows an example of the process which shows the manufacturing method of the electroconductive base material for plating. Sectional drawing of the electroconductive base material for plating which has an intermediate | middle layer, and its precursor is shown. The bottom view which shows a part of perforated metal foil which is an example of patterned metal foil. FIG. 6 is a cross-sectional view taken along the line AA ′ in FIG. 5 (however, it exists on a conductive base for plating). Sectional drawing which shows another example of patterned metal foil (however, the state which exists on the electroconductive base material for plating). The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using a rotary body.

An example of the present invention will be described with reference to the drawings.
FIG. 1 is a partial perspective view showing an example of a conductive substrate for plating according to the present invention. FIG. 2 is a cross-sectional view taken along the line AA in FIG. FIG. 2A shows a case where the side surface of the convex portion is planar, while FIG. 2B shows a case where the side surface of the convex portion has gentle irregularities. In the conductive base material 1 for plating, the insulating layer 3 is formed on the conductive base material 2, the insulating layer 3 is divergent, the concave portion 4 is formed in the insulating layer 3, and the bottom of the concave portion 4. The conductive substrate 2 is exposed. The conductive substrate 2 may be a conductor layer that is electrically connected to the conductive substrate.
In this example, the insulating layer 3 is rectangular as a geometric figure, and the recesses 4 are continuous except for the portion of the insulating layer 3.
An intermediate layer (not shown) may be laminated between the conductive substrate 2 and the insulating layer 3 for the purpose of improving the adhesiveness of the insulating layer 3 or the like. Alternatively, the recess 4 is wide as a whole in the opening direction. It is not always necessary that the width is constant and wide at the gradient α as shown in the drawing. If there is no problem in stripping the conductor layer pattern, the concave portion may have a portion whose width becomes narrower in the opening direction, but it is better not to have such a portion, and the concave portion is in the opening direction. It is preferable that it is not narrowed but spreads as a whole.

  One of the insulating layer and the concave portion has an appropriate shape depending on the purpose, and the other has a shape corresponding to this. As such shapes, as a planar shape, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a square such as a trapezoid, a (positive) hexagon, and a (positive) octagon , (Positive) dodecagons, (positive) n-decagons such as (positive) dodecagons (n is an integer greater than or equal to 3), circles, ellipses, stars, etc. The shape is selected according to the purpose The Such shapes can be used in combination. In addition, the distribution density of the insulating layer or the recess is appropriately determined according to the purpose.

  The insulating layer has a concave portion that is wide toward the opening, and correspondingly, the insulating layer has a convex shape that widens toward the bottom.

  The side surface of the recess (the side surface of the insulating layer) is not necessarily a flat surface. In this case, as shown in FIG. 2 (b), the gradient α is such that the height h of the recess (this is the thickness of the insulating layer) and the width s of the side surface of the recess (in the horizontal direction). The width direction of the side surface of the recess)

によってαを決定する。
αは、角度で３０度以上、９０度未満が好ましく、３０度以上、６０度以下が特に好ましい。この角度が小さいと作製が困難となる傾向があり、大きいと凹部にめっきにより形成し得た金属層（導体層パターン）を剥離する際の抵抗が大きくなる傾向がある。

Determines α.
α is preferably 30 ° or more and less than 90 ° in angle, and particularly preferably 30 ° or more and 60 ° or less. If this angle is small, the production tends to be difficult, and if it is large, the resistance at the time of peeling the metal layer (conductor layer pattern) formed by plating in the concave portion tends to increase.

  Further, the thickness of the insulating layer is preferably in the range of 0.1 μm to 100 μm. If the insulating layer is too thick, it takes a long time to form the insulating layer, and the working efficiency tends to decrease. In addition, if the insulating layer is too thin, pinholes are likely to be generated in the insulating layer, so that when the plating is performed, the metal is liable to be deposited on the portion provided with the insulating layer. The thickness of the insulating layer is particularly preferably 1 to 5 μm.

When the conductive substrate for plating is used to produce a perforated metal foil for a current collector for a capacitor, the insulating layer 3 as shown in FIG. The area of the contact surface is preferably 1 to 1 × 10 ⁶ square microns, and the distance between the insulating layers (the shortest distance between the protrusions) is preferably 1 to 1000 μm. The insulating layer 3 preferably has a bottom area of 1 × 10 ² to 1 × 10 ⁴ square microns, more preferably 10 to 100 μm. The area of the bottom surface of the insulating layer and the interval thereof are determined in consideration of the opening ratio of the conductor layer pattern being preferably 10% or more, particularly preferably 30% or more.
When the patterned metal foil has a through-hole, the aperture ratio is the ratio (percentage) of the hole area to the outer area of the patterned metal foil (for example, the outer area in the range in which the above geometric figure is drawn). is there.

  Examples of the shape of the conductive substrate for plating include a sheet shape, a plate shape, a roll shape, and a hoop shape. In the case of a roll, the roll itself, a sheet, or a plate may be attached to a rotating body (roll). In the case of a hoop shape, a configuration in which rolls are installed at two to several locations inside the hoop and a hoop-shaped conductive base material is passed through the roll can be considered. Since it is possible to continuously produce a metal foil in both a roll shape and a hoop shape, the production efficiency is higher than that in a sheet shape or a plate shape, which is preferable.

  The concave portion of the conductive substrate for plating corresponds to the pattern of the metal portion of the patterned metal foil, and the insulating layer corresponds to the pattern of holes (not necessarily penetrating).

  The conductive material used for the conductive substrate in the present invention has sufficient conductivity to form a conductive layer on the surface of the conductive substrate by electrolytic plating, and is particularly preferably a metal. The conductive base material is particularly preferably made of copper, stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, titanium-lined material, nickel, or the like.

  As a material of the insulating layer used in the present invention, it can be formed of carbon similar to diamond, so-called diamond-like carbon (hereinafter referred to as “DLC”) having an insulating property. DLC is particularly preferable because it is particularly excellent in chemical resistance.

As a method for forming a DLC thin film as an insulating layer, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization vapor deposition method, or a chemical vapor deposition method such as a plasma CVD method is used. A dry CVD method such as the above can be employed, but a plasma CVD method using a high frequency or pulse discharge in which the film formation temperature can be controlled from room temperature is particularly preferable.
In order to form the DLC thin film by the plasma CVD method, a hydrocarbon-based gas is preferably used as a carbon source as a raw material. For example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butene, pentene, alkadiene gases such as pentadiene, butadiene, acetylene, methylacetylene, etc. Alkyne gases, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cycloalkene gases such as cyclopentene and cyclohexene, methanol And alcohol gases such as ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as methanal and ethanal. The said gas may be used independently and may use 2 or more types together. Further, a mixture of the above-described carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and the above-described carbon source and a gas of a compound composed only of carbon and oxygen such as carbon monoxide gas and carbon dioxide gas. A mixture of a compound gas composed of only carbon and oxygen, such as a mixture, carbon monoxide gas, carbon dioxide gas, and hydrogen gas; a compound gas composed of only carbon and oxygen, such as carbon monoxide gas, carbon dioxide gas; Examples thereof include a mixture with oxygen gas or water vapor. Further, these source gases may contain a rare gas. The rare gas is a gas composed of an element belonging to Group 0 of the periodic table, and examples thereof include helium, argon, neon, and xenon. These rare gases may be used alone or in combination of two or more.

The insulating layer may be formed entirely by the above-described insulating DLC thin film, but it improves the adhesion of the DLC thin film to a conductive substrate such as a metal plate, thereby improving the durability of the insulating layer. In order to further improve, it is preferable to insert an intermediate layer composed of one or more components selected from Ti, Cr, W, Si, nitrides or carbides thereof, or the like, between the two.
The Si or SiC thin film has excellent adhesion to, for example, a metal such as stainless steel, and also forms SiC at the interface with the insulating DLC thin film laminated thereon to improve the adhesion of the DLC thin film. Has the effect of improving.
The intermediate layer can be formed by the dry coating method as described above.
The thickness of the intermediate layer is preferably 1 μm or less, and more preferably 0.5 μm or less in consideration of productivity. A coating of 1 μm or more is not suitable because the coating time becomes long and the internal stress of the coating film increases.

Even when the insulating layer is formed of an inorganic material such as Al ₂ O ₃ or SiO ₂ , a physical vapor deposition method such as a sputtering method or an ion plating method or a chemical vapor deposition method such as plasma CVD can be used. . For example, in the case of forming by sputtering, an oxide or nitride such as SiO ₂ or Si ₃ N ₄ can be formed by introducing Si or Al as a target and introducing oxygen, nitrogen or the like as a reactive gas. it can. In the case of using the ion plating method, Si or Al can be used as a raw material, and an electron beam can be irradiated to evaporate to form a film on the substrate. At that time, an oxide, nitride, or carbide film can be formed by introducing a reactive gas such as oxygen, nitrogen, or acetylene.
In the case of forming a film by the CVD method, the film can be formed by using a chemical gas such as a metal chloride, a metal hydride, an organometallic compound, etc. as a raw material. The CVD of silicon oxide can be performed by plasma CVD using, for example, TEOS or ozone. The CVD of silicon nitride can be performed by plasma CVD using ammonia and silane, for example.

As a manufacturing method of the electroconductive base material for plating in this invention, the process of forming an insulating layer so that a geometric figure may be drawn on the surface of an electroconductive base material is included.
This step includes (A) a step of forming a removable convex pattern on the surface of the conductive substrate,
(B) The process of forming an insulating layer on the surface of the electroconductive base material in which the removable convex pattern is formed, and (C) The process of removing the convex pattern to which the insulating layer has adhered are included.

The step (A) of forming a removable convex pattern on the surface of the conductive substrate can utilize a method of forming a resist pattern using a photolithographic method.
This method
(A-1) forming a photosensitive resist layer on the conductive substrate;
(A-2) including a step of exposing the photosensitive resist layer through a mask corresponding to the shape of the patterned metal foil, and (a-3) a step of developing the exposed photosensitive resist layer.

Moreover, the step of forming a removable convex pattern on the surface of the conductive substrate (A),
(B-1) a step of forming a photosensitive resist layer on the conductive substrate;
(B-2) a step of irradiating the photosensitive resist layer with a laser beam on a portion corresponding to the shape of the patterned metal foil, and (b-3) a step of developing the photosensitive resist layer after the laser beam irradiation.

  As the photosensitive resist, a well-known negative resist (a portion irradiated with light is cured) can be used. At this time, a negative mask (light passes through a portion corresponding to the convex pattern) is also used as the mask. Further, a positive resist can be used as the photosensitive resist.

  As a specific method, by laminating a dry film resist (photosensitive resin layer) on a conductive substrate, and wearing a mask to expose it, the part that remains as a convex pattern can be cured and the unnecessary part can be developed. It can be formed by developing and removing unnecessary portions. In addition, the convex pattern is a state in which the portion that remains as the convex pattern is cured by applying a liquid resist to the conductive substrate and then drying or temporarily curing the solvent, and then exposing the mask with a mask. Alternatively, the unnecessary portion can be developed, and the unnecessary portion can be developed and removed. The liquid resist can be applied by spraying, dispenser, dipping, roll, spin coating or the like.

In the above, after laminating a dry film resist or applying a liquid resist, a method of directly exposing without using a mask with a laser beam or the like instead of exposing through a mask may be employed. If the patterning can be performed by irradiating the photocurable resin with active energy rays with or without a mask, the mode is not limited.
When the size of the conductive substrate is large, a method using a dry film resist is preferable from the viewpoint of productivity. When the conductive substrate is a plating drum, the dry film resist is laminated or a liquid resist is applied. Then, a method of directly exposing with a laser beam or the like without using a mask is preferable.

An example of the manufacturing method of the electroconductive base material for plating in this invention is demonstrated using drawing.
FIG. 3 is a cross-sectional view showing an example of a process showing a method for producing a conductive substrate for plating.

  A photosensitive resist layer (photosensitive resin layer) 5 is formed on the conductive substrate 2 (FIG. 3A). The photosensitive resist layer 5 is patterned by applying a photolithographic method to the photosensitive resist layer (photosensitive resin layer) 5 of the laminate (FIG. 3B). Patterning (formation of a convex pattern) is performed by placing a photomask on which a pattern is formed on the photosensitive resist layer 5, exposing it, and developing it to remove unnecessary portions of the photosensitive resist layer 5. This is done by leaving the protrusion 6. The shape of the protruding portion 6 and the convex pattern formed therefrom are considered to correspond to the concave portion 4 on the conductive substrate 2 and the pattern.

At this time, in the cross-sectional shape of the protrusion 6, it is particularly preferable that the maximum value d ₁ of the width of the protrusion 6 is equal to or larger than the width d ₀ in contact with the protrusion 6 and the conductive substrate 2. This is because the width of the recess of the insulating layer having good adhesion is determined by d ₁ . Here, as a method of increasing the width d ₀ of the protrusion 6 in contact with the conductive substrate 2 in the cross-sectional shape of the protrusion 6, the maximum width d ₁ of the protrusion 6 is equal to or larger than the width d _0. A resist having a characteristic of sometimes over-developing or having an undercut shape may be used. It is preferable that d ₁ is realized at the upper part of the protrusion.
The shape of the protrusion 6 constituting the removable convex pattern is associated with the insulating layer 3, but from the viewpoint of ease of production, the width is 1 μm or more, the interval is 1 μm or more, and the height is 1 to 50 μm. Each is preferred.

Next, an insulating layer 7 is formed on the surface of the conductive substrate 2 having a convex pattern composed of the protrusions 6 (FIG. 3C). The method for forming the insulating layer is as described above.
Further, the protruding portion 6 is removed with the insulating layer 7 attached (FIG. 3D).
A commercially available resist stripping solution, inorganic, organic alkali, organic solvent, or the like can be used to remove the resist (protrusion 6) to which the insulating layer is attached. In addition, if there is a dedicated stripping solution corresponding to the resist used to form the pattern, it can be used.
As a peeling method, for example, it is possible to remove the resist after it has been swelled, broken or dissolved by immersion in a chemical solution. In order to sufficiently impregnate the resist with the solution, techniques such as ultrasonic waves, heating, and stirring may be used in combination. In addition, the liquid can be applied with a shower, a jet or the like in order to promote peeling, and can be rubbed with a soft cloth or cotton swab.
In addition, when the heat resistance of the insulating layer is sufficiently high, a method of baking at a high temperature to carbonize the resist and removing it, or irradiating with a laser to burn off can be used.
As the stripping solution, for example, a 3% by mass NaOH solution is used, and a shower or immersion can be applied as the stripping method.

The property differs between the insulating layer formed on the conductive substrate 2 and the insulating layer formed on the side surface of the protrusion 6. For example, the hardness of the former is greater than the latter. In the formation of the insulating layer, the conductive base material does not become a shadow of the resist, so that the insulating layer on the conductive base material has a uniform property. On the other hand, the insulating layer is formed on the side surface of the protruding portion 6 because the side surface of the protruding portion 6 has an angle with respect to the film thickness direction on the conductive substrate. As for the film, an insulating layer having the same characteristics (for example, the same hardness) as the insulating layer on the conductive substrate cannot be obtained. In such a heterogeneous insulating layer contact surface, a boundary surface of the insulating layer is formed as the insulating layer grows, and the boundary surface is a growth surface of the insulating layer, and is smooth. For this reason, when the protrusion 6 is removed, the insulating layer (particularly the DLC film) is easily separated at this boundary. Furthermore, the boundary surface, that is, the inclination angle α which becomes the side surface of the protrusion 6 is inclined because the growth of the insulating layer is delayed on the side surface of the protrusion 6 with respect to the film thickness direction on the conductive substrate. To be controlled.
The inclination angle α of the side surface of the recess is preferably 30 ° or more and less than 90 °, particularly preferably 30 ° or more and 60 ° or less. However, when the DLC film is formed by the plasma CVD method, the inclination of the side surface of the recess is The angle α is easily controlled to an angle of about 45 to 60 degrees. That is, the concave portion 4 is formed so as to become wider toward the opening direction.

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. The insulating layer having a hardness of less than 10 GPa is soft, and when the conductive substrate is used as a plating plate, durability in repeated use is reduced. A hardness of 40 GPa or more is not preferable because when the conductive substrate is processed such as bending, it cannot follow the deformation of the substrate and cracks and cracks occur in the insulating layer. More preferably, it is 12-30 GPa.
On the other hand, the hardness of the insulating layer formed on the side surface of the protrusion is preferably 1 to 15 GPa. The insulating layer formed on the side surface of the protrusion must be formed so as to be at least lower in hardness than the insulating layer formed on the conductive substrate. By doing so, a boundary surface is formed between the two, and a convex insulating layer that spreads toward the bottom surface is formed after the process of peeling the convex pattern composed of the protrusions to which the insulating layer is attached later. It will be. As for the hardness of the insulating layer formed in the side surface of a projection part, it is more preferable that it is 1-10 GPa.

The hardness of the insulating layer can be measured using a nanoindentation method. In the nanoindentation method, a regular triangular pyramid (Berkovic) indenter with a diamond tip is pressed into the surface of a thin film or material, and the hardness is obtained from the load applied to the indenter and the projected area under the indenter. As a measurement by the nanoindentation method, a device called a nanoindenter is commercially available. The hardness of the film formed on the conductive substrate can be measured by pressing an indenter from the conductive substrate as it is. In addition, in order to measure the hardness of the film formed on the side surface of the convex part, a part of the conductive substrate is cut out and cast with resin, and the indenter is pushed into the insulating layer formed on the side surface of the convex part from the cross section. Can be measured. Normally, in the nanoindentation method, the hardness is measured by applying a minute load of 1 to 100 mN to the indenter, but in the present invention, the value measured by applying a load of 3 mN for 10 seconds is described as the hardness value.
Thus, the electroconductive base material 1 for plating can be produced.

FIG. 4 shows a cross-sectional view of a conductive substrate for plating having an intermediate layer and its precursor.
It is preferable to form the intermediate layer 8 on the surface of the conductive substrate 2 on which the convex pattern composed of the protrusions 6 is formed, before forming the insulating layer 7 (FIG. 4 (c ′)). As the intermediate layer, those described above can be used, and the formation method is also as described above. When the intermediate layer 8 is formed, the conductive substrate 2 for plating obtained is exposed from the conductive substrate 2, and otherwise the insulating layer 7 is formed on the intermediate layer 8 (FIG. 4). (D ′)). Further, the intermediate layer may be formed on the surface of the conductive substrate 2 before the convex pattern is formed. Then, you may perform the process of forming an insulating layer so that a geometric figure may be drawn on the surface of the electroconductive base material 2 as mentioned above on the surface. In this case, when an intermediate layer is used that is sufficiently conductive for electrolytic plating, the surface of the conductive substrate 2 may remain as the intermediate layer, but does not have sufficient conductivity. In such a case, the intermediate layer on the surface of the conductive substrate 2 is removed by a method such as dry etching to expose the conductive substrate 2.

  In the conductive base material for plating of the present invention, the insulating layer formed on the surface has a convex shape that spreads out, but this forms a convex pattern that can be removed on the surface of the conductive base material. Since the convex pattern to which the insulating layer is attached can be removed after forming the film, its manufacture is easy and the productivity is high. For the same reason, according to the method for producing a conductive substrate for plating of the present invention, the number of steps is small, and in particular, a convex shape with a diverging insulating layer can be easily produced. Can be manufactured.

  The patterned metal foil in the present invention corresponds to the shape of the conductive substrate for plating described above, and as a planar shape, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, and a parallelogram Shapes, trapezoids and other quadrangles, (positive) hexagons, (positive) octagons, (positive) dodecagons, (positive) n-decagons (n is an integer of 3 or more), circles, These are metal foils with through-holes such as ellipses and stars, metal foils with recesses of this shape, individually separated metal foils of such shape, etc. In order to facilitate peeling, a continuous foil is preferable even when there are through holes. The shape is selected according to the purpose. Such shapes can be used in combination. Further, the size and distribution density of the through holes or the recesses are appropriately determined according to the purpose.

FIG. 5 is a bottom view showing a part of a perforated metal foil which is an example of a patterned metal foil. In the figure, six pairs of circles each composed of three concentric circles are drawn, and these are repeated in a zigzag manner at an appropriate number of times in the horizontal and vertical directions. FIG. 6 shows an AA ′ cross-sectional view in FIG. 5, and FIG. 6 shows a state in which the patterned metal foil is present on the conductive substrate for plating.
A hole 10 passes through the patterned metal foil 9. Around the hole 10, there is a stepped portion 11 and an inclined portion 12 having a small width following the stepped portion 11. The step portion 11 and the inclined portion 12 correspond to the insulating layer 3 on the conductive substrate 2 and the concave portion on the conductive substrate 2 formed thereby, and the inclined portion 12 corresponds to the insulating layer 3. It is formed corresponding to the inclined part that spreads toward the end. That is, in FIG. 6, the inclined portion 12 has an inner circumference (minimum diameter) and an outer circumference (maximum diameter), but is inclined from an inner circumference having a small diameter (an end of the stepped portion 11) toward an outer circumference having a large diameter. doing.
The step portion 11 corresponds to a portion formed so that plating covers the insulating layer 3 from the concave portion of the conductive base material for plating. Therefore, since the thickness of the patterned metal foil 9 in the step portion 11 is a portion formed so as to cover the insulating layer 3, the portion closer to the hole 10 has a smaller thickness. It becomes higher by the thickness of the insulating layer 3 than the bottom surface of the patterned metal foil corresponding to the concave portion which is the plating portion.

FIG. 7 is a cross-sectional view showing another example of the patterned metal foil, and shows a state existing on the conductive substrate for plating as in FIG. The plating deposited in the recesses on the conductive substrate 2 grows so as to run on the insulating layer 3 and has no through hole, but becomes a patterned metal foil 9 having a recess corresponding to the insulating layer 3. Fine grooves can be formed in the patterned metal foil by extending the insulating layer 3 in the front and back direction of the paper and reducing the width. By closing the groove with an appropriate material so that the inside is not filled, a fine liquid or gas flow path can be easily formed. Accordingly, the present invention can be applied to a heat sink, a supply channel for a small amount of drug, and the like.
In addition, as said appropriate material, flat metal foil without a groove | channel or a recessed part, said patterned metal foil itself (The groove | channel is opposed, or the surface which passes a groove | channel is opposed, but a groove | channel does not overlap. A plurality of the patterned metal foils may be laminated in the same direction, and the surface including the last exposed groove can be closed with an appropriate material.

In the present invention, the patterned metal foil is
(A) a step of depositing a metal by plating in the concave portion of the conductive substrate for plating,
And (b) manufactured by a method including a step of peeling the metal deposited in the concave portion of the conductive substrate.

A well-known method can be employ | adopted for the plating method in this invention. As the plating method, an electrolytic plating method, an electroless plating method, or other plating methods can be applied.
The electrolytic plating will be further described. For example, in the case of electrolytic copper plating, a copper sulfate bath, a copper borofluoride bath, a copper pyrophosphate bath, a copper cyanide bath, or the like can be used as an electrolytic bath for plating. At this time, it is known that the dispersion of electrodeposition stress can be further reduced by adding a stress relieving agent (also having an effect as a brightener) due to organic matter or the like to the plating bath. For electrolytic nickel plating, a Watt bath, a sulfamic acid bath, or the like can be used. In order to adjust the flexibility of the nickel foil in these baths, additives such as saccharin, paratoluenesulfonamide, sodium benzenesulfonate, sodium naphthalene trisulfonate, and commercial additions that are preparations as necessary An agent may be added. Furthermore, in the case of electrolytic gold plating, alloy plating using potassium gold cyanide, pure gold plating using an ammonium citrate bath or a potassium citrate bath, or the like is used. In the case of alloy plating, a gold-copper, gold-silver, gold-cobalt binary alloy or a gold-copper-silver ternary alloy is used. Similarly, other known methods can be used for other metals. As the electrolytic plating method, for example, “Practical Plating for On-Site Engineers” (edited by the Japan Plating Association, published by Sakai Shoten in 1986), pages 87 to 504 can be referred to.

Next, the electroless plating will be further described. Typical examples of the electroless plating method include copper plating and nickel plating, but other examples include tin plating, gold plating, silver plating, cobalt plating, and iron plating. In the process of electroless plating used industrially, a reducing agent is added to a plating solution, and electrons generated by the oxidation reaction are used for metal precipitation reaction. , Reducing agent, pH adjusting agent, pH buffering material, stabilizer and the like. In the case of electroless copper plating, copper sulfate is preferably used as the metal salt, formalin as the reducing agent, and Rossel salt or ethylenediaminetetraacetic acid (EDTA) as the complexing agent. Moreover, although pH is mainly adjusted with sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be used, carbonate and phosphate are used as a buffer, and monovalent as a stabilizer. Cyanide, thiourea, bipyridyl, o-phenanthroline, neocuproine, etc. that preferentially complex with copper are used. In the case of electroless nickel plating, nickel sulfate is preferably used as the metal salt, and sodium hypophosphite, hydrazine, a borohydride compound, or the like is preferably used as the reducing agent. When sodium hypophosphite is used, phosphorus is contained in the plating film, and the corrosion resistance and wear resistance are excellent. Moreover, as a buffering agent, a monocarboxylic acid or its alkali metal salt is often used. As the complexing agent, one that forms a stable soluble complex with nickel ions in the plating solution is used, and acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycine, alanine, EDTA, etc. are used. In this case, sulfur compounds and lead ions are added. Regarding the electroless plating method, the above-mentioned pages 505 to 545 can be referred to.
Furthermore, in order to obtain the reducing action of the reducing agent, it may be necessary to activate the catalyst on the metal surface. When the substrate is a metal such as iron, steel, nickel, etc., these metals have catalytic activity, so they are deposited just by immersing them in the electroless plating solution, but copper, silver or their alloys, and stainless steel In this case, in order to impart catalyst activation, a method is used in which the object to be plated is immersed in an acidic hydrochloric acid solution of palladium chloride and palladium is deposited on the surface by ion substitution.

The electroless plating that can be used in the present invention is, for example, immersed in an electroless copper plating solution at a temperature of about 60 to 90 ° C. after a palladium catalyst is adhered to the surface of the conductive base material for plating, if necessary. This is a method of performing copper plating.
In electroless plating, the substrate is not necessarily conductive. However, when anodizing the substrate, the substrate needs to be conductive.
In particular, when the material of the conductive substrate is Ni, electroless plating includes a method in which the surface is anodized and then immersed in an electroless copper plating solution to deposit copper.

As a metal that appears or precipitates by plating, conductive metals such as silver, copper, gold, aluminum, tungsten, nickel, iron, and chromium are used, but the volume resistivity (specific resistance) at 20 ° C. is used. It is desirable to include at least one kind of metal of 20 μΩ / cm or less. This is because when the structure obtained according to the present invention is used as an electromagnetic wave shielding sheet, the metal constituting it is grounded as an electromagnetic wave as a current, and the higher the conductivity, the better the electromagnetic wave shielding property. Such metals include silver (1.62 μΩ / cm), copper (1.72 μΩ / cm), gold (2.4 μΩ / cm), aluminum (2.75 μΩ / cm), tungsten (5.5 μΩ / cm). ), Nickel (7.24 [mu] [Omega] / cm), iron (9.0 [mu] [Omega] / cm), chromium (17 [mu] [Omega] / cm, all values at 20 [deg.] C.), etc., but are not particularly limited thereto. If possible, the volume resistivity is more preferably 10 μΩ / cm or less, and further preferably 5 μΩ / cm or less. In view of the price of metal and availability, copper is most preferably used. These metals may be used alone, or may be an alloy with another metal or a metal oxide for imparting functionality. However, from the viewpoint of conductivity, it is preferable that a metal having a volume resistivity of 20 μΩ / cm or less is contained in the largest amount as a component.
The thickness (plating thickness) of the metal layer formed by plating on the surface of the conductive substrate described above is preferably 0.5 μm or more in order to exhibit sufficient conductivity, and is pinned on the metal foil. In order to reduce the possibility that holes are formed, the thickness is more preferably 3 μm or more. Sufficient electrical conductivity is important when using a patterned metal foil as a current collector for a capacitor.

The thickness of the metal foil formed by plating is reduced from the viewpoint that the deposited metal layer can be regulated more in shape by making the recess deeper relative to the thickness of the deposited metal layer. The height of the insulating layer is preferably 2 times or less, particularly preferably 1.5 times or less, and further preferably 1.2 times or less, but is not limited thereto.
The degree of plating can be such that the deposited metal layer is present in the recess. Even in such a case, since the concave shape is wide in the opening direction, and furthermore, the surface of the concave side surface formed by the insulating layer can be smoothed, the anchor effect when peeling the metal foil pattern is extremely Can be small. Moreover, it becomes possible to make high the ratio of the height with respect to the width | variety of the metal layer to deposit, and to improve the transmittance | permeability more.

  After plating using the conductive substrate for plating, the patterned metal foil can be obtained by peeling the patterned metal foil formed on the substrate. In this case, as the substrate for peeling, a substrate in which an adhesive layer is laminated on another substrate is used, and the adhesive is applied to the metal foil surface of the plating conductive substrate on which the patterned metal foil is formed. To the contrary, after the base material for peeling is pressure-bonded, it is peeled off, the patterned metal foil is transferred to the base material for peeling, and the patterned metal foil can be peeled from the electroconductive substrate for plating. The patterned metal foil is appropriately obtained by peeling from the peeling substrate.

  As described above, a rotating body (roll) can be used as the conductive base material used in the present invention. The rotating body (roll) is preferably made of metal. Furthermore, it is preferable to use a drum electrode or the like used in the drum-type electrolytic deposition method as the rotating body. As described above, the material that forms the surface of the drum electrode may be a material with relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. preferable. By using a rotating body as the conductive base material, it is possible to obtain a base material with a conductor layer pattern as a roll, and in this case, productivity is greatly increased.

  A process of obtaining a structure as a scroll while continuously peeling a pattern formed by electrolytic plating using a rotating body will be described with reference to FIG. FIG. 8 shows the concept of an apparatus for continuously depositing metal by electrolytic plating while continuously rotating the drum electrode when using a drum electrode as the conductive substrate, and continuously stripping the deposited metal. It is sectional drawing (partial front view) shown.

That is, the electrolytic solution 101 in the electrolytic bath 100 is supplied to the space between the anode 102 and the rotating body 103 such as a drum electrode by the pipe 104 and the pump 105. When a voltage is applied between the anode 102 and the rotator 103 and the rotator 103 is rotated at a constant speed, metal is electrolytically deposited on the surface of the rotator 103, and the conductivity of the surface of the rotator 103 is outside the electrolytic solution 101. The adhesive layer of the peeling film 107 on which the adhesive layer is formed is pressure-bonded to the metal 106 deposited in the recesses of the metal 106 with the pressure roll 108, and the adhesive layer is formed on the surface while continuously peeling the metal 106 from the rotating body 103. The metal 106 is transferred to the peeling film 107 that is present, and a peeling film 109 having the metal 106 transferred thereon is obtained. This can be wound up on a roll (not shown). Note that the metal 106 may be peeled from the rotating body 103 without using the peeling film 107 and the pressure roll 108.
Note that an insulating layer is formed on the surface of the rotating body 103, and there is a concave portion that is a plating portion corresponding to the insulating layer. Further, the surface of the rotating body 103 may be etched and cleaned (not shown) after the metal 106 deposited in the concave portion is peeled off from the rotating rotating body 103 and before being immersed in the electrolytic solution 101. . Although not shown, a draining roll may be installed at the upper end of the anode 102 in order to prevent the electrolyte circulating at high speed from being ejected upward. The electrolyte stopped by the draining roll is the anode 102. Return to the bottom electrolyte bath from outside and circulated by the pump. Further, although not shown, it is preferable to add a mode in which a copper ion source and additives consumed during the circulation are added as necessary.

Furthermore, as described above, a hoop-like conductive base material can be used as the conductive base material used in the present invention.
The hoop-like conductive base material can be produced by forming an insulating layer and a recess on the surface of the belt-like conductive base material and then joining the end portions. As described above, the material forming the surface of the conductive substrate is made of a material having relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. It is preferable. When a hoop-like conductive substrate is used, the process of blackening treatment, rust prevention treatment, transfer, etc. can be processed in one continuous process, so the productivity of the patterned metal foil is high, Moreover, a patterned metal foil can be produced continuously to obtain a product as a roll. The thickness of the hoop-like conductive substrate may be determined as appropriate, but is preferably 100 to 1000 μm.

  Further, the patterned metal foil in the present invention is not limited to the continuous plating method using the rotating roll and the hoop as described above, and can be manufactured as a single sheet. When performed in a single wafer, it is easy to handle when preparing a conductive substrate for plating, and even when the same insulating layer is peeled off after repeated use of the same conductive substrate for plating, it is drum-shaped. In the case of a hoop-shaped substrate, it is difficult to extract or replace only a specific portion. However, if it is a sheet, it is possible to extract or replace only the conductive substrate for plating in which a defect has occurred. In this way, by making a single wafer, it is easy to handle when a problem occurs in the conductive substrate for plating. The thickness of the sheet-like conductive base material may be determined as appropriate, but the thickness is preferably 20 μm or more in consideration of giving sufficient strength not depending on the stirring of the liquid in the plating tank. If it is too thick, the weight increases and it is difficult to handle, so a thickness of 10 cm or less is preferable.

(Formation of convex pattern)
A resist film (Photech RY3315, 15 μm thick, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 150 mm square stainless steel plate (SUS316L, mirror polished, thickness 300 μm, manufactured by Nisshin Steel Co., Ltd.) (FIG. 3). Corresponding to (a)). The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the diameter of the circular pattern which is a light-impermeable portion is 100 μm, the pitch of the circular pattern is 150 μm, and the arrangement of the circular patterns is staggered (circular pattern rows are arranged in a staggered manner for each row). The formed negative film was allowed to stand on one side of a stainless steel plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the stainless plate on which the negative film was placed under a vacuum of 600 mmHg or less. further. By developing with a 1% by mass aqueous sodium carbonate solution, protrusions with a diameter of 98 to 99 μm (thickness 15 μm) and a convex pattern of resist films arranged in a staggered manner with a protrusion pitch of 150 μm were formed on the SUS plate. . These numerical values were determined by observing at least 5 points with an optical microscope. The above-mentioned diameter is the maximum diameter (d ₁ ) of the protrusion and is the diameter at the top of the protrusion. The diameter of the contact portion of the protrusion with the conductive substrate was 0 to about 1 μm smaller than the maximum diameter. In addition, the minimum diameter of the protrusion is 0 to about 2 μm smaller than the maximum diameter, and is a diameter of a portion slightly higher than the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.
In addition, since the entire surface opposite to the surface on which the pattern is formed is exposed, it is not developed and a resist film is formed on the entire surface.

(Formation of insulating layer)
A DLC film was formed using a PBII / D apparatus (Type III, manufactured by Kurita Manufacturing Co., Ltd.). That is, a stainless steel substrate with a resist film attached thereto was put in the chamber, the inside of the chamber was evacuated, and then the substrate surface was cleaned with argon gas. Next, hexamethyldisiloxane was introduced into the chamber, and an intermediate layer was formed to a thickness of 0.1 μm. Subsequently, toluene, methane, and acetylene gas were introduce | transduced and the DLC layer was formed on the intermediate | middle layer so that a film thickness might be set to 5-6 micrometers (corresponding to FIG.3 (c)). At that time, the thickness of the DLC film on both sides of the resist pattern formed by the resist film was 4 to 6 μm. The angle of the boundary surface was 45 to 51 degrees. The thickness of the insulating layer and the angle of the boundary surface were measured by cutting a part of the conductive base material, casting it with resin, and observing the cross section with a magnification of 3000 times. Since the measurement points were 5 points and both sides of the resist film were measured, a maximum value and a minimum value of 10 points in total were adopted.

(Removal of resist pattern with insulating layer and formation of insulating layer pattern)
The stainless steel substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10 mass%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film and the DLC film attached thereto were peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating (corresponding to FIG. 3D).
When observed in the same manner as the SEM observation, the shape of the insulating layer of the conductive substrate for plating is a convex shape spreading toward the bottom, and the inclination angle of the side surface of the protruding insulating layer is It was similar to the interface angle. The height of the insulating layer was 5 to 6 μm. The diameter of the bottom surface of the insulating layer was 98 to 99 μm, and the diameter (minimum diameter) of the top surface of the insulating layer was 86 to 91 μm. The pitch of the insulating layer was 150 μm. These numerical values were determined by observing at least 5 points with an optical microscope.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed.
Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 250 g / L, sulfuric acid 70 g / L, sulfuric acid 70 g / L, cube) using the electroconductive substrate for plating with the adhesive film attached as a cathode and phosphorus-containing copper as an anode Immerse it in 4 ml / L aqueous solution (30 ° C), light AR (supplied by Ebara Eugelite Co., Ltd.), apply voltage to both electrodes to set the current density to 10 A / dm ² and apply it to the surface of the conductive substrate for plating Plating was performed until the deposited metal had a thickness of approximately 20 μm. As a result, the copper foil was formed so as to cover the exposed surface of the conductive substrate and the end of the insulating layer (see FIG. 6).

(Peeling)
The copper foil formed on the electroconductive substrate for plating was peeled off. Thereby, the copper foil in which the pattern which has the pattern which the hole of diameter 57-60 micrometers is arrange | positioned at a hole pitch of 150 micrometers in zigzag was given was obtained. These numerical values were determined by observing at least 5 points with an optical microscope. The shape of the copper foil to which this pattern is applied has a step portion 11 around the hole reflecting the shape of the insulating layer as shown in FIG. 6, and the inclined portion 12 following the step portion 11 is In the bottom view, it was inclined from the outer periphery with a large diameter toward the inner periphery with a small diameter.
As a result of observing the surface of the conductive substrate for plating after peeling, there was no place where the insulating layer was peeled off.

(Repeated use)
Next, using the conductive substrate for plating, the copper plating-copper foil peeling process was repeated 500 times in the same manner as described above. As a result, there was no change in the transferability of the copper plating, and the peeling portion of the insulating layer was Not observed.

(Formation of convex pattern)
A liquid resist (ZPN-2000, manufactured by Nippon Zeon Co., Ltd.) was applied on both sides to a 150 mm square titanium plate (pure titanium, mirror polished, thickness 400 μm, manufactured by Nippon Metal Co., Ltd.). By applying three times, a resist film having a thickness of 6 μm was obtained. After prebaking at 110 ° C. for 1 minute, the diameter of the circular pattern, which is a light-impermeable portion, is 50 μm, the interval between the circular patterns is 70 μm, and the circular pattern is arranged in a staggered manner (the circular pattern rows are staggered in each row). The negative mask in which the pattern is formed with a size of 110 mm square was left on one side of the titanium plate. The substrate was adsorbed under a vacuum of 600 mmHg or less using an ultraviolet irradiation device, and ultraviolet rays were irradiated at 200 mJ / cm ² from the top of the titanium plate on which the negative mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 115 ° C. for 1 minute and developing with 2.38 mass% tetramethylammonium hydroxide (TMAH), protrusions with a diameter of 49-50 μm (thickness 6 μm) on the titanium plate, protrusion pitch A convex pattern of resist film arranged in a staggered pattern with a thickness of 70 μm was formed. The diameter and pitch were measured in the same manner as in Example 1. The above-mentioned diameter is the maximum diameter (d ₁ ) of the protrusion and is the diameter at the top of the protrusion. The diameter of the contact portion between the protrusion and the conductive substrate was measured in the same manner as in Example 1. As a result, it was 0 to 0.5 μm smaller than the maximum diameter. Further, the minimum diameter of the protrusion is 0 to about 1 μm smaller than the maximum diameter, and is a diameter of a portion slightly higher than the contact portion of the protrusion with the conductive substrate.

(Formation of insulating layer)
After coating to the intermediate layer as in Example 1, DLC was coated to a thickness of 2 to 2.5 μm. At this time, the thickness of the DLC film on both sides of the pattern formed by the resist film was 1.8 to 2.5 μm. The angle of the boundary surface was 45 to 47 degrees. The film thickness and the interface angle were measured in the same manner as in Example 1.

(Removal of resist pattern with insulating layer and formation of insulating layer pattern)
The titanium substrate to which the insulating layer was adhered was immersed in an aqueous sodium hydroxide solution (10 mass%, 50 ° C.) and left for 2 hours while applying ultrasonic waves at 50 kHz. The resist film and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating.
When the SEM observation was performed in the same manner as in Example 1, the shape of the insulating layer of the conductive base material for plating spreads toward the bottom, and the inclination angle of the side surface of the convex portion was the same as the angle of the boundary surface. Met. The height of the insulating layer was 2 to 2.5 μm. Further, when measured in the same manner as in Example 1, the diameter of the bottom of the insulating layer was 49 to 50 μm, and the diameter (minimum diameter) of the top of the insulating layer was φ44 to 46 μm. The pitch of the insulating layer was 70 μm.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. An electrolysis bath for electrolytic copper plating using the conductive substrate for plating with the adhesive film attached as a cathode and a copper plate as an anode (copper pyrophosphate: 100 g / L, potassium pyrophosphate: 250 g / L, aqueous ammonia ( 30 mass%): 2 mL / L, pH: 8-9, bath temperature: 30 ° C.), a voltage is applied to both electrodes to set the cathode current density to 5 A / dm ² , and the surface of the conductive substrate for plating is applied. Plating was performed until the deposited metal had a thickness of approximately 20 μm. As a result, the copper foil was formed so as to cover the surface of the conductive substrate and the end of the insulating layer (see FIG. 6).

(Peeling)
The copper foil provided with the pattern formed on the electroconductive substrate for plating was peeled off. When measured in the same manner as in Example 1, a copper foil provided with a pattern having a pattern in which holes having a diameter of 8 to 11 μm were arranged in a staggered manner at a pitch of 70 μm was obtained. The shape of the copper foil to which this pattern is applied has a step portion 11 around the hole reflecting the shape of the insulating layer as shown in FIG. 6, and the inclined portion 12 following the step portion 11 is In the bottom view, it was inclined from the outer periphery with a large diameter toward the inner periphery with a small diameter.
As a result of observing the surface of the conductive substrate for plating after peeling, there was no place where the insulating layer was peeled off.

(Repeated use)
Next, as a result of repeating the copper plating-peeling process 700 times in the same manner as described above using the conductive base material for plating, there is no change in the transferability of the copper plating, and the peeled portion of the insulating layer is also observed. There wasn't.

(Formation of convex pattern)
A liquid resist (KMPR-1050, manufactured by Nippon Kayaku Co., Ltd.) was applied to both surfaces of a stainless steel substrate (SUS304, 314 × 150 mm, manufactured by Nisshin Steel Co., Ltd.) with a thickness of 10 μm. After pre-baking at 90 ° C. for 10 minutes, the diameter of the circular pattern which is a light-impermeable portion is 60 μm, the pitch of the circular pattern is 80 μm, and the arrangement of the circular patterns is staggered (the circular pattern rows are staggered for each column). 2), two negative masks having a pattern formed in a size of 110 mm square were placed side by side on one side of a stainless steel plate and allowed to stand. Using a UV irradiation device, the substrate was adsorbed under a vacuum of 600 mmHg or less, and 200 mJ / cm ^{2 of} UV was irradiated from above the stainless steel plate on which the negative mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 95 ° C. for 7 minutes and developing with 2.38% by mass of tetramethylammonium hydroxide (TMAH), protrusions with a diameter of 59 to 60 μm and protrusion pitch of 80 μm are staggered on a stainless steel plate. A convex pattern of the aligned resist film was formed. The diameter and pitch were measured in the same manner as in Example 1. The above-mentioned diameter is the maximum diameter (d ₁ ) of the protrusion and is the diameter at the top of the protrusion. The diameter of the contact portion between the protrusion and the conductive substrate was measured in the same manner as in Example 1. As a result, it was 0 to about 0.8 μm smaller than the maximum diameter. Further, the minimum diameter of the protrusion is 0 to about 1.5 μm smaller than the maximum diameter, and is a diameter of a portion slightly higher than the contact portion of the protrusion with the conductive substrate.

(Formation of insulating layer)
As in Example 2, DLC was coated to a thickness of 3 to 4 μm. At this time, the thickness of the DLC film on both sides of the resist pattern formed by the resist film was 2.7 to 4 μm. The angle of the boundary surface was 45 to 48 degrees.

(Removal of resist pattern with insulating layer and formation of insulating layer pattern)
The stainless steel substrate on which the insulating layer was adhered was immersed in a resist stripping solution (RemoverPG, Nippon Kayaku Co., Ltd., 70 ° C.) and left for 8 hours with occasional rocking. The resist film and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating.
When observed by SEM as in Example 1, the shape of the insulating layer was divergent, and the angle of inclination of the side surface of the insulating layer was the same as the angle of the boundary surface. The height of the insulating layer was 3-4 μm. Moreover, when measured similarly to Example 1, the diameter of the bottom part of the insulating layer was 59 to 60 μm, and the diameter of the upper part of the insulating layer (minimum diameter) was 51 to 54 μm. The pitch of the insulating layer was 80 μm.

(Copper plating)
A stainless steel roll having a diameter of 100 mm and a width of 200 mm was wound so that the back surface of the conductive substrate for plating produced above and the roll were in contact with each other, and a joint was bonded with an insulating tape. Furthermore, the roll and the conductive base material were bonded together so as to cover the entire circumference of the conductive base material 5 mm with the insulating tape so that the plating solution did not penetrate from the side portion, thereby forming one rotating body.
Next, electrolytic copper plating was performed on the rotating body 103 with an apparatus configuration as shown in FIG. As the anode 102, an insoluble electrode made of titanium coated with platinum was used. The stainless steel roll was used as the drum electrode for the cathode. In the electrolytic bath 100 for electrolytic copper plating, copper pyrophosphate: 100 g / L, potassium pyrophosphate: 250 g / L, aqueous ammonia (30% by mass): 2 mL / L, pH: 8-9 with an aqueous solution of 40 ° C. The electrolytic solution 101 is accommodated, and is sent and filled between the anode 102 and the rotating body 103 by the pump 105 through the pipe 104. About half of the rotating body 103 is immersed in the electrolytic solution. A voltage was applied to both electrodes so that the current density was 15 A / dm ^2, and plating was performed until the thickness of the metal deposited on the conductive substrate became 20 μm. At this time, the stainless steel roll was rotated at a speed of 0.1 m / min. As a result, the copper foil was formed so as to cover the surface of the conductive substrate and the end of the insulating layer.

(Peeling)
The copper pattern formed on the electroconductive substrate for plating was peeled off. A copper foil provided with a pattern having a hole diameter of 18 to 21 μm and a hole pitch of 80 μm was obtained. The shape of the copper foil to which this pattern is applied has a step portion 11 around the hole reflecting the shape of the insulating layer as shown in FIG. 6, and the inclined portion 12 following the step portion 11 is In the bottom view, it was inclined from the outer periphery with a large diameter toward the inner periphery with a small diameter.
As a result of observing the surface of the conductive substrate for plating after peeling, there was no place where the insulating layer was peeled off.

(Repeated use)
Using the conductive substrate for plating transfer obtained above, the copper plating-peeling process was repeated 5000 times in the same manner as described above (the rotating body was rotated 5000 times), resulting in a change to the peelability of copper plating. There was no separation of the insulating layer.

(Formation of convex pattern) to (Removal of resist pattern with insulating layer attached and formation of insulating layer pattern)
In the same manner as in Example 1, a convex pattern was formed on a stainless steel plate, an insulating layer was formed, a resist pattern to which the insulating layer adhered was removed, and an insulating layer pattern was formed to produce a conductive substrate for plating. .

(Copper plating)
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the convex pattern of the conductive substrate for plating obtained above was not formed. Electrolytic baths for electrolytic copper plating (copper sulfate (pentahydrate) 255 g / L, sulfuric acid 55 g / L, sulfuric acid 55 g / L, cube) using the conductive substrate for plating with the adhesive film attached as a cathode and phosphorus-containing copper as an anode Immersion in light # 1A (supplied by EBARA Eugelite Co., Ltd., 4 ml / L aqueous solution, 20 ° C.), voltage applied to both electrodes to set the cathode current density to 7 A / dm ² , Plating was performed until the thickness of the metal deposited on the surface was approximately 70 μm. The copper plating covered the insulating layer, and the plated state was as shown in FIG.

(Peeling)
The copper foil provided with the pattern formed on the electroconductive substrate for plating was peeled off. The pattern formed on the copper foil is formed as a circular recess in the copper foil, and has a recess entrance diameter of 98 to 99 μm, a recess bottom diameter of 86 to 91 μm, and a circular recess pitch of 150 μm. As shown in FIG. 2, the concave portion was narrowed from the entrance to the bottom surface reflecting the shape of the insulating layer. The diameter and pitch were measured at 5 points or more with an optical microscope.
As a result of observing the surface of the conductive substrate for plating after peeling, there was no place where the insulating layer was peeled off.

(Repeated use)
Next, as a result of repeating the copper plating-transfer process 700 times in the same manner as described above using the above-described conductive substrate for plating, there was no change in the transfer property of the copper plating, and the peeling portion of the insulating layer was also observed. There wasn't.

(Comparative Example 1)
(Hole pattern formation)
A convex pattern was formed in the same manner as in Example 1 to obtain a hole pattern having a diameter of 98 to 99 μm and a pitch of 150 μm. At that time, one end of the surface of the conductive substrate was left unexposed so that the base metal was exposed after development.

(Formation of insulating layer)
Next, the conductive substrate on which the resist pattern is formed is used as a cathode, and the portion where the above-mentioned base metal is exposed is connected to the electrode with a clip, and the anode is a stainless steel (SUS304) plate, and a cationic electrodeposition paint (Insulated 3020). , Manufactured by Nippon Paint Co., Ltd.), the conductive substrate was electrodeposited on the condition of 15V for 10 seconds. After washing with water and drying at 110 ° C. for 10 minutes, an insulating layer was formed by baking under a nitrogen stream at 230 ° C. for 40 minutes. The oxygen concentration in the furnace was 0.1%. The height of the insulating layer formed on the flat portion was about 2 to 3 μm. The electrodeposition paint is not deposited on the resist pattern because it is not originally energized, but the electrodeposition paint adhering to the resist film could not be cleaned, so both sides of the resist pattern formed by the resist film An electrodeposition coating film was also attached to the surface, and the thickness was 0.2 to 0.7 μm. In the case of the electrodeposition paint, the boundary surface between the side surface portion of the resist pattern and the film formed on the flat portion was not formed.

(Removal of resist pattern with insulating layer)
The stainless steel substrate coated with the electrodeposition paint was immersed in an aqueous sodium hydroxide solution (10% by mass, 50 ° C.) and left for 15 minutes with occasional shaking. The resist film forming the convex pattern and the electrodeposition paint adhering thereto have been peeled off. Although the side surface portion of the insulating layer had various shapes, there were many places where the insulating layer was not formed in a divergent shape, and the boundary surface of the insulating layer was not smooth but many places with broken surfaces were seen. Further, the shape of the insulating layer was somewhat fluctuated.

(Copper plating)
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the convex portion of the conductive base material for plating obtained above was not formed. Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 70 g / L, sulfuric acid 180 g / L, sulfuric acid 180 g / L, capalaside) using the conductive substrate for plating with the adhesive film attached as a cathode and phosphorous copper as an anode HL (manufactured by Atotech Japan Co., Ltd., additive), 20 ° C.), a voltage is applied to both electrodes, the current density is 8 A / dm ² , and the thickness of the metal deposited on the surface of the conductive substrate for plating is Plating was performed until the thickness became approximately 20 μm.

(Peeling)
The copper pattern formed on the electroconductive substrate for plating was peeled off. A copper foil provided with a pattern having a hole diameter of 57 to 60 μm and a hole pitch of 150 μm was obtained once, but the hole pattern had a backlash and a clean pattern could not be obtained.
(Repeated use)
Then, using the conductive substrate for plating, the copper plating-peeling process was repeated in the same manner as described above. As a result, the peeled portion of the insulating layer was visually recognized at the seventh time.

  Table 1 shows the characteristic values of plating conductive substrates obtained in Examples 1 to 4 and Comparative Example 1, plating conditions, characteristics of conductor layer patterns, and the like.

1: Conductive substrate for plating 2: Conductive substrate 3: Insulating layer 4: Recessed portion 5: Photosensitive resist layer (photosensitive resin layer)
6: Convex pattern (projection)
7: DLC film (insulating layer)
8: Intermediate layer 9: Patterned metal foil 10: Hole (through hole)
DESCRIPTION OF SYMBOLS 11: Step part 12: Inclined part 100: Electrolytic bath 101: Electrolyte solution 102: Anode 103: Rotating body 104: Piping 105: Pump 106: Metal 107: Film for peeling 108: Crimp roll 109: Release film with which the metal was transferred

Claims (7)

(A) An electroconductive substrate for plating in which an insulating layer is formed on the surface of the electroconductive substrate, and a concave portion is formed in the insulating layer that is wide toward the opening direction and exposes the electroconductive substrate. Depositing metal on the surface of the metal by plating,
(B) a metal foil obtained by a method for producing a metal foil provided with a pattern comprising a step of peeling the metal deposited on the surface of the conductive substrate for plating,
In the conductive substrate for plating, the insulating layer is formed so as to draw a geometric figure or to draw a geometric figure itself,
The insulating layer of the conductive substrate for plating is made of diamond-like carbon (DLC) , Al ₂ O ₃ or SiO ₂ ,
In the plating electrically conductive substrate, the angle of the concave side is more than 30 degrees with the insulating layer side state, and are 60 degrees or less,
The recess forms a removable convex pattern on the surface of the conductive substrate, after the formation of the insulating layer, Ru der those made by removing the convex pattern insulating layer is adhered, Metal foil. The metal foil obtained by the manufacturing method of the metal foil with which the pattern of Claim 1 which the hardness of the insulating layer of the electroconductive base material for plating consists of 10-40 GPa DLC was given. 2. The electroconductive substrate for plating, wherein the insulating layer has a convex shape with an area of a bottom surface of 1 to 1 × 10 ⁶ square microns, and the convex shape is distributed at intervals of 1 to 1000 μm. Or the metal foil obtained by the manufacturing method of the metal foil in which the pattern of 2 was given. The metal foil obtained by the manufacturing method of the metal foil with which the pattern in any one of Claims 1-3 was given in the electroconductive base material for plating whose thickness of an insulating layer is 0.1-100 micrometers. 2. An electroconductive substrate for plating, wherein an intermediate layer containing at least one of Ti, Cr, W, Si, or a nitride or carbide thereof is interposed between the conductive substrate and the insulating layer. The metal foil obtained by the manufacturing method of the metal foil in which the pattern in any one of 4 was given. The metal foil obtained by the manufacturing method of the metal foil in which the pattern in any one of Claims 1-5 in which the surface of the electroconductive base material consists of steel or Ti in the electroconductive base material for plating. The conductive substrate for plating is wound around a conductive roll (drum) or a roll. Metal foil obtained by the method for producing a metal foil provided with the pattern according to any one of claims 1 to 6 .

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