JP2009158842A - Manufacturing method for surface-blackening copper metal, manufacturing method for base material with conductor-layer pattern, base material with conductor-layer pattern and electromagnetic-wave shielding member using base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a surface-blackening copper metal being capable of manufacturing a base material with a conductor-layer pattern with an excellent productivity by using a transfer method and facilitating a manufacture, the manufacturing method for the base material with the conductor-layer pattern, the base material with the conductor-layer pattern and an electromagnetic-wave shielding member using the base material. <P>SOLUTION: A process in which copper metallic layers are formed by depositing copper metals to recessed sections 4 formed in broad widths towards the opening direction to insulating layers 3 formed to the surface of the conductive base material 2 under a first current density and the copper metal is deposited on a copper surface in a black or a brown under a second current density larger than the first current density is conducted in one copper-sulfate plating bath. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a substrate with a conductor layer pattern patterned so as to have excellent electrical conductivity and light transmittance, a substrate with a conductor layer pattern, and an electromagnetic wave shielding member using the same.

In general, a copper foil performs an electrolytic reaction while supplying a predetermined electrolytic solution containing these metal ions between an insoluble cathode body and an insoluble anode body, to thereby obtain a target metal of the cathode body. It is manufactured by depositing a metal conductor layer as a foil by electrodepositing a desired thickness on the surface, and then peeling the formed metal conductor layer from the surface of the cathode body. In this case, a drum-shaped or plate-shaped cathode body is used.
It is known that the copper foil thus obtained is blackened on the surface for the purpose of erasing the gloss of the surface and improving the adhesion to the resin.

  Examples of the copper foil include a patterned copper foil such as a mesh copper foil used for electromagnetic wave shielding, in addition to a solid copper foil such as a copper foil used as a material for a copper clad laminate.

  Various methods have been proposed for shielding electromagnetic waves on the walls of public facilities, halls, hospitals, schools, corporate buildings, houses, etc., glass windows, resin panels, display surfaces of displays that generate electromagnetic waves, and the like. For example, a method of applying an electromagnetic shielding coating over the surface to be shielded, a method of bonding a metal foil on the surface to be shielded, an electromagnetic shielding sheet formed by thermally laminating a metal-plated fiber mesh on a resin plate, In general, a method of bonding to a surface, a method of bonding conductive fibers knitted in a mesh shape to a surface to be shielded, and the like are performed.

Among these, when shielding the electromagnetic wave on the transparent glass surface, the transparent resin panel surface, the display surface of a display such as a cathode ray tube (CRT) or a plasma display panel (PDP), the electromagnetic shielding member is required to be as thin as possible. In addition, an electromagnetic wave shielding member having a metal mesh as an electromagnetic wave shielding layer has become mainstream as a light balance (transparency) and an electromagnetic wave shielding property opposite to this in a balanced manner. .
The metal mesh used as the electromagnetic wave shielding member is desired to have a dark color with no gloss for the purpose of improving the visibility of the display surface, and therefore needs to be blackened.
In Patent Document 1, two or more anodes are arranged with respect to one drum-like cathode while using the same electrolytic solution, and the drum-like cathode is immersed in the plating bath by about half and rotated. Then, after making a copper foil with the first current density, a method for producing a solid plating of a solid copper foil by subsequently applying a second current density and precipitating copper on the fine particles on the surface. It is disclosed. However, a geometric figure made of a conductor for a transparent electromagnetic wave seed member is not disclosed.

  In Patent Document 2, a metal electrolyte is electrodeposited on an electrodeposition substrate capable of metal electrodeposition in a mesh shape, and an electromagnetic wave shielding plate is produced by adhesive transfer to an electromagnetic wave shielding substrate via an adhesive. How to do is described. The above-mentioned electrodeposition substrate is formed on a conductive substrate such as a metal plate with a pattern opposite to the mesh pattern made of an insulating film that inhibits electrodeposition. As a result, metal electrodeposition in a mesh shape is possible. It is produced so that a simple electrodeposition portion is exposed. When this electrodeposition substrate is used, it can be used repeatedly several times to several tens of times, but there is a problem that it cannot be used several hundred times to several thousand times and does not reach a mass production level. This is because the insulating film forming the mesh pattern on the electrodeposition substrate is subjected to peeling stress by adhesion transfer, and the insulating film is peeled off from the electroconductive substrate for plating after a few repeated uses.

  In the method for producing an electromagnetic wave shielding plate using the transfer method described in Patent Document 2, the step of performing metal electrodeposition and the step of blackening are separate steps. The solution used in the metal electrodeposition step and the solution used in the blackening step are usually not allowed to mix with each other in the plating tank, and cannot be performed in the same plating tank. Therefore, sufficient water washing and further a blackening treatment pretreatment step may be required, and the time, cost, and environmental load required for production are not small.

Japanese translation of PCT publication No. 2002-506484 JP 11-119675 A

The present invention relates to a method for efficiently producing a patterned copper metal layer or patterned copper metal having a blackened surface.
The present invention also includes a step of electrodeposition depositing a patterned copper metal layer on a conductive substrate for plating and a step of efficiently blackening the surface of the deposited copper metal layer. Another object is to provide a method for producing a substrate with a conductor layer pattern with good productivity.
In these methods, the present invention further provides a method in which the electrodeposition substrate (conductive substrate for plating) can withstand repeated use and is excellent in mass productivity.
This invention provides the manufacturing method of the base material with a conductor layer pattern in which the transfer of the electrodeposited metal is performed more smoothly in the manufacturing method of the base material with a conductor layer pattern.
The present invention also provides a substrate with a conductor layer pattern, which is obtained by such a method and has excellent electromagnetic shielding properties and light transmission properties, and an electromagnetic shielding member using the same.

The present invention relates to the following.
1. In the method of manufacturing a patterned copper metal layer whose surface is blackened using a conductive substrate for plating, the conductive substrate for plating has an insulating layer formed on the surface of the conductive substrate. A conductive substrate having a recess pattern for forming a plating that is wide in the opening direction in the insulating layer, and a first current density is formed in the recess of the conductive substrate for plating. A conductive layer forming step of depositing copper metal underneath to form a copper metal layer, and the surface of the copper metal layer under a second current density larger than the first current density, the surface being black or A method for producing a patterned copper metal layer having a blackened surface, wherein a blackening treatment step of depositing copper metal so as to become brownish brown is performed in one copper sulfate plating bath.
2. The surface according to item 1, wherein the conductive layer forming step is performed in the first electrodeposition region including the first current density, and the blackening treatment step is performed in the second electrodeposition region including the second current density. For producing a patterned copper metal layer.
3. In the blackening treatment process, with a background of black having a lightness of 25, copper metal is used so that the light transmission portion having an aperture ratio of 50% has a lightness of 25 to 50, or chromaticity a * and b * are both 5 or less. The manufacturing method of the patterned copper metal layer by which the surface of the term 1 or 2 to deposit was blackened.
4). Item 1 or 2 in which, in the blackening treatment step, metal is deposited so that the aperture ratio is 40% or more and the chromaticity a * and b * of the light transmission part are both 2.8 or less with a black background of 25 lightness. The manufacturing method of the patterned copper metal layer by which the surface of description was blackened.
5. In the blackening treatment step, the metal is applied so that the aperture ratio is less than 40% and the chromaticity a * and b * of the light transmitting portion or the light non-transmitting portion with a lightness of 25 as a background is both 5 or less. The manufacturing method of the patterned copper metal layer by which the surface of the term 1 or 2 to deposit was blackened.
6). Item 6. The method for producing a patterned copper metal layer having a blackened surface according to any one of Items 1 to 5, wherein the copper sulfate plating bath is a plating bath containing a surfactant as an additive.
7). The manufacturing method of the patterned copper metal layer by which the surface of any one of claim | item 1-6 whose 1st current density is 0.5-40 A / dm < ² > was blackened.
8). In any one of Items 1 to 7, in the conductive substrate for plating, the recess for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself. The manufacturing method of the patterned copper metal layer by which the surface of description was blackened.
9. The manufacturing method of the patterned copper metal layer by which the surface of any one of claim | item 1-8 which an insulating layer consists of diamond-like carbon (DLC) or an inorganic material in the electroconductive base material for plating was blackened .
10. Item 10. The method for producing a patterned copper metal layer, wherein the surface of the conductive substrate for plating is blackened on the surface according to Item 9, wherein the insulating layer is DLC, Al ₂ O ₃ or SiO ₂ .
11. Item 11. The method for producing a patterned copper metal layer, wherein the surface of the conductive substrate for plating is blackened in Item 10, wherein the insulating layer is made of DLC having a hardness of 10 to 40 GPa.
12 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. The manufacturing method of the patterned copper metal layer by which the surface of any one of 11 was blackened.
13. Item 13. The surface according to any one of Items 1 to 12, wherein in the conductive base material for plating, the minimum width of the recess is 1 to 40 μm, the maximum width of the recess is 2 to 60 μm, and the interval between the recesses is 50 to 1000 μm. A method for producing a patterned copper metal layer that has been processed.
14 The pattern by which the surface of any one of claim | item 1-13 whose surface angle of a recessed part is 10 degree or more and less than 90 degree | times with respect to a base material by the side of an insulating layer in the conductive base material for plating was blackened A method for producing a copper chloride metal layer.
15. The pattern by which the surface of any one of claim | item 1-14 whose surface angle of a recessed part is 10 degree or more and 80 degrees or less with respect to a base material by the side of an insulating layer in the electroconductive base material for plating was blackened. A method for producing a copper chloride metal layer.
16. Item 16. The method for producing a patterned copper metal layer having a blackened surface according to any one of Items 1 to 15, wherein the conductive substrate for plating has a thickness of the insulating layer of 0.5 to 20 µm.
17. The manufacturing method of the patterned copper metal layer by which the surface of any one of claim | item 1 -16 whose surface of a conductive base material consists of steel or Ti in the conductive base material for plating was blackened.
18. The manufacturing method of the patterned copper metal layer by which the surface of any one of claim | item 1 -17 whose electroconductive base material for plating is a rotary body or the flat plate attached to the rotary body was blackened.
19. As the conductive substrate, a conductive substrate made of a rotating body or a conductive substrate attached to the rotating body is used, a part of the substrate is immersed in a plating solution, and while rotating the rotating body, a metal pattern manufacturing step and The manufacturing method of the patterned copper metal by which the surface of any one of claim | item 1-17 which performs a transcription | transfer process was blackened.
20. Item 20. The patterned copper metal whose surface according to any one of items 1 to 19, wherein the copper metal is deposited so that the thickness of the copper metal is 0.1 to 20 μm in the copper metal layer forming step. Layer manufacturing method.
21. A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black A second anode for performing a blackening treatment step for depositing a metal so as to become brownish brown is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. The manufacturing method of the patterned copper metal layer by which the surface of any one of claim | item 1-20 characterized by the blackening process was provided.
22. A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black The second anode for performing the blackening treatment step for depositing the metal so as to become brownish brown is also used, and after the formation of the conductive layer under the first current density, the second anode Item 20. The method for producing a patterned copper metal layer having a blackened surface according to any one of Items 1 to 19, wherein the blackening step is performed under a current density.
23. After performing the manufacturing method of the copper metal layer by which the surface in any one of claim | item 1-22 was blackened, peeling the copper metal layer by which the surface was blackened from the electroconductive base material for plating A method for producing a patterned copper metal having a blackened surface.
24. An insulating layer is formed on the surface of the conductive substrate, and a recess is formed on the insulating layer to form a wide plating in the opening direction. In the method for producing a substrate with a conductor layer pattern, including a metal pattern preparation step of depositing copper metal by plating and a transfer step of transferring the copper metal deposited on the conductive substrate to an adhesive support,
A conductive layer forming step in which a metal pattern forming step forms a copper metal layer under a first current density; and a surface of the copper metal layer under a second current density greater than the first current density. A method for producing a substrate with a conductor layer pattern, wherein a blackening treatment step for depositing a metal so that the surface is black or brown is performed in one copper sulfate plating bath.
25. Item 25. The conductive layer patterned base according to Item 24, wherein the conductive layer forming step is performed in the second electrodeposition region including the first current density, and the blackening treatment step is performed in the second electrodeposition region including the second current density. A method of manufacturing the material.
26. In the blackening treatment step, copper metal is deposited so that the light transmission portion having an aperture ratio of 50% has a lightness of 25 to 50, or both a * and b * are 5 or less against a black background of lightness 25. Item 26. A method for producing a substrate with a conductor layer pattern according to Item 24 or 25.
27. Item 24 or 25 in which the metal is deposited in the blackening treatment step so that the aperture ratio is 40% or more and the chromaticity a * and b * of the light transmission part are both 2.8 or less with a black background of brightness 25 The manufacturing method of the base material with a conductor layer pattern of description.
28. In the blackening treatment step, the metal is applied so that the aperture ratio is less than 40% and the chromaticity a * and b * of the light transmitting portion or the light non-transmitting portion with a lightness of 25 as a background is both 5 or less. Item 26. A method for producing a substrate with a conductor layer pattern according to Item 24 or 25.
29. Item 29. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 28, wherein the copper sulfate plating bath is a plating bath containing a surfactant as an additive.
30. Item 30. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 29, wherein the first current density is 0.5 to 40 A / dm ² .
31. Item 31. The substrate with a conductor layer pattern according to any one of Items 24 to 30, wherein the recess for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself. Manufacturing method.
32. Item 32. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 31, wherein the insulating layer is made of diamond-like carbon (DLC) or an inorganic material.
33. Item 33. The method for producing a substrate with a conductor layer pattern according to Item 32, wherein the insulating layer is DLC, Al ₂ O ₃ or SiO ₂ .
34. Item 34. The method for producing a substrate with a conductor layer pattern according to Item 33, wherein the insulating layer is made of DLC having a hardness of 10 to 40 GPa.
35. Item 35. The item 24 to 34, wherein an intermediate layer containing any one or more of Ti, Cr, W, Si, nitrides or carbides thereof is interposed between the conductive substrate and the insulating layer. The manufacturing method of the base material with a conductor layer pattern.
36. Item 36. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 35, wherein the minimum width of the recesses is 1 to 40 μm, the maximum width of the recesses is 2 to 60 μm, and the interval between the recesses is 50 to 1000 μm.
37. Item 37. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 36, wherein an angle of the side surface of the recess is 10 degrees or more and less than 90 degrees with respect to the substrate on the insulating layer side.
38. 40. The method for producing a substrate with a conductor layer pattern according to Item 37, wherein the angle of the side surface of the recess is 10 degrees or more and 80 degrees or less with respect to the substrate on the insulating layer side.
39. 40. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 38, wherein the insulating layer has a thickness of 0.5 to 20 μm.
40. Item 40. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 39, wherein the surface of the conductive substrate is made of steel or Ti.
41. Item 41. The method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 40, wherein the conductive substrate is a rotating body or a flat plate attached to the rotating body.
42. As the conductive substrate, a conductive substrate made of a rotating body or a conductive substrate attached to the rotating body is used, a part of the substrate is immersed in a plating solution, and the rotating body is rotated, while the metal pattern preparation step and 42. The manufacturing method of the base material with a conductor layer pattern of any one of claim | item 24-41 which performs a transcription | transfer process.
43. Item 43. The conductor layer pattern according to any one of Items 24 to 42, wherein, in the conductive layer forming step, the metal is deposited so that the thickness of the metal is 0.1 to 20 µm on the upper surface of the convex portion of the conductive substrate. A method for producing a substrate.
44. In the method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 43,
A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black A second anode for performing a blackening treatment step for depositing a metal so as to become brownish brown is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. The manufacturing method of the base material with a conductor layer pattern characterized by the above-mentioned.
45. In the method for producing a substrate with a conductor layer pattern according to any one of Items 24 to 43,
A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black The second anode for performing the blackening treatment step for depositing the metal so as to become brownish brown is also used, and after the formation of the conductive layer under the first current density, the second anode The manufacturing method of the base material with a conductor layer pattern characterized by performing the said blackening process process under an electric current density.
46. Item 46. A substrate with a conductor layer pattern, produced by the method according to any one of Items 24 to 45.
47. Item 49. A light-transmitting electromagnetic wave shielding member obtained by bonding a surface having a conductor layer pattern of a substrate with a conductor layer pattern according to Item 46 to a transparent substrate.
48. Item 49. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 46 with a resin.

  According to the present invention, since the preparation of the patterned copper metal layer and the blackening treatment of the surface thereof can be performed in one plating bath, the patterned copper metal layer or the blackened surface of the copper metal layer or Copper metal can be produced with high productivity. Thereby, a base material with a conductor layer pattern can also be produced with high productivity.

  Since the recessed part which is a plating formation part of the conductive base material for plating in this invention is wide toward the opening direction, peeling of the deposited copper metal is easy. Further, when the insulating layer on the surface of the conductive substrate for plating is DLC or an inorganic material, particularly DLC, the durability is particularly excellent. Therefore, the production efficiency of the copper metal layer or copper metal whose surface has been blackened and the substrate with the conductor layer pattern is excellent.

  Metallic rotating body as conductive substrate, or copper metal layer patterned and blackened by electrically connecting conductive substrate to metallic rotating body Moreover, since the transfer of the metal layer to the adhesive support can be performed, the production efficiency of the copper metal layer or copper metal whose surface is further blackened and the substrate with the conductor layer pattern is improved.

  Moreover, in this invention, since the plating formation part is a recessed part, it can perform the blackening process without a powder fall uniformly regardless of a thin wire | line part and a wide part in a series of processes. Thereby, it becomes possible to shorten the metal pattern production process including the conductor layer forming process and the blackening process. By suitably controlling the deposition conditions of black or brown metal in the second electrodeposition region, the black or brown metal can be deposited in a granular or lumpy shape, whereby a good blackening treatment without powder falling can be performed.

  The electromagnetic wave shielding body obtained using the conductive layer pattern is excellent in light transmittance. For this reason, when used as an electromagnetic wave shielding body of a display, a clear image can be comfortably viewed without adversely affecting the body due to electromagnetic waves without increasing the luminance. In addition, since the electromagnetic wave shielding body is excellent in electromagnetic wave shielding properties, it is required to be transparent, especially for a display or other device that generates electromagnetic waves, or a measuring device that is protected from external electromagnetic waves, a measuring instrument or a manufacturing device. It is very effective if it is used at a site such as a viewing window. Furthermore, the electromagnetic wave shielding body in the present invention can be produced with high production efficiency as in the case of the substrate with a conductor layer pattern.

  The conductor layer pattern can be protected by laminating a transparent substrate on the surface having the conductor layer pattern of the substrate with the conductor layer pattern, or by coating with a transparent resin. In the case where an adhesive layer is formed in advance on the conductor layer transfer surface of another base material, it also has an effect of preventing foreign matter from adhering to the adhesive layer. At this time, the transparent substrate can be bonded by pressing the transparent substrate directly or through another adhesive to the adhesive layer. In this case, since the conductor layer pattern is embedded in the adhesive layer with an appropriate pressure, it is possible to improve transparency and adhesion to the transparent substrate.

  By using a transparent substrate with a conductor layer pattern, it is possible to easily obtain an electromagnetic wave shielding body having both high light transmittance (particularly, the line width of the conductor layer pattern is small and high definition) and good conductivity (high electromagnetic shielding properties). it can. For this reason, when used as an electromagnetic wave shield for a display such as a PDP, a clear image can be comfortably viewed under almost the same conditions as in a normal state without increasing the luminance. In addition, since the electromagnetic wave shielding body is excellent in electromagnetic wave shielding properties, a display or other device that generates electromagnetic waves, or a window or housing that looks into the inside of a measuring device, measuring device, manufacturing device, etc. that should be protected from electromagnetic waves, In particular, the effect is great if it is used by being provided in a part such as a window or display surface where transparency is required. Furthermore, the production method of the electromagnetic wave shielding body according to the present invention is excellent in production efficiency as in the production of the conductor layer pattern.

The metal mesh used as the electromagnetic wave shielding member is desired to have a non-glossy dark color for the purpose of improving the visibility of the display surface. Therefore, it is generally necessary to perform a blackening treatment. The blackness in the blackening process is preferably completely black, but good blackness is not necessarily required due to the advancement of manufacturing technology and management technology of the electromagnetic wave shielding member or the filter or display device including the electromagnetic shielding member. Therefore, in the present invention, the black color may be a dark color tone that can erase the gloss of the surface and suppress reflection, that is, a brownish brown color.
The conductive substrate for plating in the present invention is a conductive substrate having a pattern-shaped plating forming portion, and an insulating layer is formed on the surface of the conductive substrate, and the insulating layer faces the opening direction. And a concave portion (plating forming portion) for forming a wide plating. The conductive material is exposed on the bottom surface of the recess.

  In the present invention, the conductive material used for the conductive substrate has sufficient conductivity for depositing metal on the exposed surface by electrolytic plating, and is particularly preferably a metal. In addition, the base material has a low adhesion to the metal layer formed on it so that the metal layer formed by electrolytic plating on the surface can be transferred to the adhesive support, and can be easily peeled off. It is preferable that As such a conductive base material, stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, titanium-lined material, nickel and the like are particularly preferable.

  Examples of the shape of the conductive substrate include a sheet shape, a plate shape, a roll shape, and a hoop shape. In the case of a roll, a sheet or plate attached to a rotating body (roll) may be used. 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. When the conductive substrate is used by being wound around a roll, a conductive roll is preferably used so that the roll and the conductive substrate are easily conducted.

  The thickness of the insulating layer corresponds to the depth of the recess. Since the depth of the recess is related to the thickness of the plating to be deposited, it is appropriately determined according to the purpose. The thickness of the insulating layer is preferably in the range of 0.10 μm to 100 μm, and more preferably in the range of 0.5 μm to 20 μm. The thickness of the insulating layer is particularly preferably 1 to 10 μm. 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 likely to be deposited on the portion where the insulating layer is applied. From such a viewpoint, the thickness of the insulating layer is particularly preferably 1 μm or more, and particularly preferably 3 μm or more.

The insulating layer can be formed of a carbon thin film similar to diamond, a so-called diamond-like carbon (hereinafter referred to as DLC) thin film having an insulating property. The DLC thin film is particularly preferable because it is excellent in durability and chemical resistance.
Furthermore, the insulating layer can be formed of an inorganic material such as an inorganic compound such as Al ₂ O ₃ or SiO ₂ .

The shape of the recess or the insulating layer is appropriately determined according to the purpose, but the planar shape is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or a quadrangle ( (Positive) Hexagons, (Positive) Octagons, (Positive) Dodecagons, (Positive) N-gons (n is an integer of 3 or more), circles, ellipses, stars, etc. There are academic figures, and these units may be appropriately combined. These units can be repeated alone or in combination of two or more. In one conductive substrate for plating, the shape of the concave portion and the shape of the insulating layer are shapes corresponding to each other.
From the viewpoint of the performance of the light-transmitting electromagnetic wave shielding member, it is most effective to make the insulating layer surrounded by the groove-like recesses triangular, and from the viewpoint of visible light transmission, if the groove-like recesses have the same line width When the insulating layer surrounded by it is a (positive) n-gon, the larger the n number, the higher the aperture ratio of the conductor layer pattern.

An example of the conductive substrate for plating 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 recess is a flat surface, while FIG. 2B shows a case where the side surface of the recess has gentle irregularities. In the conductive base material 1 for plating, the insulating layer 3 is laminated on the conductive base material 2, and the concave portion 4 is formed in the insulating layer 3. Exposed. The bottom of the recess 4 may be a conductor layer made of a conductive material that is electrically connected to the conductive substrate.
In this example, the insulating layer 3 has a square shape as a geometric figure, and a recess 4 is formed in a groove shape around the square.
A conductive or insulating 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 peeling of the metal layer (conductor layer pattern) formed by plating, the recess may have a portion whose width becomes narrower in the opening direction, but there is no such portion. It is preferable that the concave portion is not narrowed toward the opening direction but widens as a whole.

によってαを決定する。
αは、角度で１０度以上９０度未満が好ましく、１０度以上８０度以下がより好ましく、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、３０度以上がより好ましく、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、又は、別の基材に転写する際の抵抗が大きくなる傾向があり、８０度以下がより好ましい。 The side surface of the recess is not necessarily a flat surface. In this case, as shown in FIG. 2B, the gradient α is determined by the height h of the recess (in many cases, defined by the thickness of the insulating layer) and the width s (horizontal) of the side surface of the recess. In the direction of the width of the side surface of the recess)

Determines α.
α is preferably 10 degrees or more and less than 90 degrees, more preferably 10 degrees or more and 80 degrees or less, and particularly preferably 30 degrees or more and 60 degrees or less. If this angle is small, the production tends to be difficult, and 30 degrees or more is more preferable. If it is large, the metal layer (conductor layer pattern) that can be formed by plating in the concave portion is peeled off or on another substrate. Resistance at the time of transfer tends to increase, and 80 degrees or less is more preferable.

The planar shape of the insulating layer and the thickness of the insulating layer or the depth of the recess in the conductive substrate for plating of the present invention are appropriately determined according to the use of the patterned metal obtained using the conductive substrate for plating of the present invention. Is done.
The concave portion of the conductive base material for plating corresponds to the shape of the patterned metal generated by plating, and the conductor layer pattern is similarly so as to correspond to the conductor layer pattern in the base material with the conductor layer pattern. Finally, it can correspond to the electromagnetic wave shielding layer when the electromagnetic wave shielding member is produced.

  In addition, the thickness of the insulating layer is the same as described above. In order to correspond to this, the depth of the recess 4 in the conductive substrate for plating of the present invention is preferably 0.1 to 100 μm. 0.5 to 20 μm is more preferable, and 1 to 10 μm is particularly preferable.

When using the conductive substrate for plating of the present invention to produce a member for applications requiring light transmittance or transparency, such as a light transmissive electromagnetic wave shielding member and a transparent antenna, by a transfer method, The width of the recess 4 as shown in FIG. 2 is preferably such that the width d of the opening is 2 to 60 μm and the width d ′ of the bottom is 1 to 40 μm. The width d of the opening of the recess 4 is particularly preferably 4 to 15 μm, and the width d ′ of the bottom is particularly preferably 3 to 10 μm. The center interval (line pitch) of the recesses 4 is preferably 50 to 1000 μm, and particularly preferably 100 to 400 μm. The width of the groove and the interval between the grooves are determined considering that the opening ratio of the conductor layer pattern is preferably 50% or more, particularly preferably 80% or more.
In the present invention, the center interval (line pitch) of the recesses cannot be easily determined because the figure pattern of the insulating layer formed by the recesses is a complicated figure or a combination of a plurality of figures. Is defined as the length of one side of the pattern by converting the area into a square area based on the repeating unit of the pattern.

  From the viewpoint of visible light transmittance in the electromagnetic wave shielding material for display, the conductive layer pattern aperture ratio for drawing the geometric figure as described above in the electromagnetic wave shielding material is required to be 50% or more. The aperture ratio is more preferably 80% or more. The aperture ratio of the conductor layer pattern is the effective area of the electromagnetic wave shielding material or the like (for example, the area of the range in which the geometric figure is drawn, such as the area that functions effectively in the electromagnetic wave shielding or the like). It is the percentage of the ratio of the area obtained by subtracting the area covered with the conductive layer from the effective area.

When used to produce a perforated metal foil using the conductive substrate for plating of the present invention, the insulating layer 3 as shown in FIG. 2 has its bottom surface (contact surface with the conductive substrate). 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. Such a perforated metal foil is useful as a current collector of a capacitor.

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

As the step of forming a removable convex pattern on the surface of the conductive substrate (A), a method of forming a resist pattern using a printing method or a photolithographic method can be used.
When using the photolithographic method, this method is
(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 a concave pattern serving as a plating formation portion, and (a-3) a step of developing the exposed photosensitive resist layer (the above method “a Law ").

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 without masking a portion corresponding to the concave pattern serving as a plating formation portion; and (b-3) developing the photosensitive resist layer after the laser beam irradiation. Step to remove (unnecessary part of photosensitive resist)
(Referred to as “method b” above).

  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 concave portion) is also used as the mask. Further, a positive resist can be used as the photosensitive resist. Corresponding to these methods, the light irradiation part in the method a and method b is appropriately determined.

  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, it is also possible to employ a method of directly exposing without using a mask with a laser beam or the like instead of exposing through a mask. 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.

  In the method b, a thermosetting resin can be used instead of the photosensitive resist, and an unnecessary portion of the thermosetting resin can be removed by laser light irradiation.

  Although a resist pattern (convex pattern) can be formed by using a printing method, in this case, various methods can be used as a resist pattern printing method. For example, screen printing, letterpress printing, letterpress offset printing, letterpress reversal offset printing, intaglio printing, letterpress printing, ink jet printing, flexographic printing, and the like can be used. As the resist, a photocurable or thermosetting resin can be used. After printing, the resist is cured by light irradiation or heat.

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 is performed by placing a photomask on which a pattern is formed on the photosensitive resist layer 5, exposing it, developing it, removing unnecessary portions of the photosensitive resist layer 5, and leaving protrusions 6. Done. 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, the side surface is perpendicular to the conductive base material, or the end of the protrusion 6 is in contact with the end where the protrusion 6 contacts the conductive base 2. It is preferable to be in a position where at least a part of the upper side surface covers the end portion. In terms of the width of the protrusion 6, the maximum value d ₁ of the convex pattern width is preferably equal to or larger than the width d ₀ that contacts the convex pattern and the conductive substrate 2. This is because the concave width 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 that sometimes over-develops or has 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 that forms the removable convex pattern is associated with the shape of the recess. From the ease of production, the maximum width is 1 μm or more, the interval is 1 μm or more, and the height is 1 to 50 μm. Preferably there is. When the electroconductive substrate for plating is used in an application requiring light transparency or transparency, such as a conductor layer pattern used for a light transmissive electromagnetic wave shielding member or a transparent antenna, the protrusion 6 is It is preferably 1 to 40 μm, the interval is 50 to 1000 μm, and the height is 1 to 30 μm. In particular, it is preferable that the maximum width is 3 to 10 μm and the interval is 100 to 400 μm. Further, when the conductive substrate for plating is used for producing a perforated metal foil, the planar shape is a circular or rectangular shape having an appropriate size so that the insulating layer 3 as described above is formed. Are arranged at appropriate intervals.

The step (B) of forming an insulating layer on the surface of the conductive substrate on which the removable convex pattern is formed will be described.
An insulating layer 7 is formed on the surface of the conductive substrate 2 (see FIG. 3B) having a convex pattern composed of the protrusions 6 (see FIG. 3C).

  As a method for forming a DLC thin film as an insulating layer, a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, a physical vapor deposition method such as an ionization deposition method, a chemical vapor deposition method such as a plasma CVD method, etc. However, the plasma CVD method using a high frequency or pulse discharge in which the film forming 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. Also, a mixture of the above-mentioned carbon source and hydrogen gas as a source gas containing carbon and hydrogen as elements, and a mixture of the above-mentioned carbon source and a compound gas consisting only of carbon and oxygen, such as carbon monoxide gas and dioxide gas. , A mixture of a compound gas composed of only carbon and oxygen, such as carbon monoxide gas and carbon dioxide gas, and a hydrogen gas, a compound gas composed of only carbon and oxygen, such as carbon monoxide gas and carbon dioxide gas, and oxygen Examples thereof include a mixture with 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 an inorganic compound 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 may be used. 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.

Next, the step (C) of removing the convex pattern to which the insulating layer is attached will be described. With the insulating layer 7 attached (see FIG. 3C), the convex pattern is removed (see FIG. 3D).
A commercially available resist stripping solution, inorganic, organic alkali, organic solvent, or the like can be used to remove the resist 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% NaOH solution is used, and showering or dipping can be applied as the stripping method.

The insulating layer formed on the conductive substrate 2 and the insulating layer formed on the side surface of the protruding portion 6 are made to have different properties or characteristics. For example, the hardness of the former is greater than that of the latter. This is the case when the DLC film is formed by plasma CVD. In general, when an insulating film is formed, when the moving speed of the insulating material is different by, for example, an angle of 90 degrees, the properties or characteristics of the film formed as described above are different.
When the protrusion 6 is removed, the insulating layer is separated at this boundary, and as a result, the side surface of the recess has an inclination angle α. The inclination angle α is preferably 10 degrees or more and less than 90 degrees, more preferably 10 degrees or more and 80 degrees or less, further preferably 30 degrees or more and 60 degrees or less, particularly preferably 40 degrees or more and 60 degrees or less, and the DLC film is plasma-treated. In the case of manufacturing by CVD, it becomes easy to control to about 40 to 60 degrees. That is, the concave portion 4 is formed so as to become wider toward the opening direction. As a method of controlling the inclination angle α, a method of adjusting the height of the protrusion 6 is preferable. As the height of the protrusion 6 increases, the inclination angle α can be controlled more greatly.

  In the formation of the insulating layer, the conductive base material does not become a shadow of the resist, and therefore the insulating layer on the conductive base material has uniform properties. On the other hand, the insulating layer is formed on the side surface of the convex pattern because the side surface of the convex pattern 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 convex pattern consisting of the protrusions is removed, the insulating layer (particularly the DLC film) is easily separated at this boundary. Furthermore, the inclination angle α that becomes the boundary surface, that is, the side surface of the concave portion is that the growth of the insulating layer is delayed on the side surface of the protruding portion with respect to the film thickness direction on the conductive substrate. , Controlled as described above.

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. An insulating layer having a hardness of less than 10 GPa is soft and has a low durability when repeatedly used as a conductive substrate for plating. 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 lower than at least the hardness of the insulating layer formed on the conductive substrate. By doing so, a boundary surface is formed between the two, and a wide concave portion is formed after a step of peeling the convex pattern to which the insulating layer is attached later. The hardness of the insulating layer formed on the side surface of the protrusion is more preferably 1 to 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 consisting of 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 protrusion, a part of the conductive substrate is cut out and cast with a resin, and an indenter is pushed into the insulating layer formed on the side surface of the protrusion 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 base material for plating obtained is such that the conductive base material 2 is exposed at the bottom of the recess 4, and otherwise, the insulating layer 7 is formed on the intermediate layer 8. (FIG. 4 (d ′)). The intermediate layer may be formed on the surface of the conductive substrate 2 before the convex pattern 6 is formed. Then, you may perform the process of forming an insulating layer on the surface so that a geometric figure may be drawn by the recessed part which has exposed the electroconductive base material as mentioned above. In this case, when an intermediate layer is used that is sufficiently conductive for electroplating, the bottom of the recess may remain the intermediate layer, but if it does not have sufficient conductivity, The intermediate layer at the bottom of the recess is removed by a method such as etching to expose the conductive substrate 2.

Using the conductive substrate for plating. Electrolytic plating is applied to the plating forming portion.
A copper sulfate bath is used as the plating bath in the present invention. The copper sulfate bath is an electrolytic solution containing copper sulfate and sulfuric acid. Specific examples thereof include those having the following composition.

Copper sulfate (pentahydrate) 50-400 g / L (12-100 g / L as copper content)
Sulfuric acid 50-200 g / L
An aqueous solution in which chlorine ions, surfactants, brighteners and the like are dissolved and blended is used as necessary. Examples of the chlorine ion source include hydrochloric acid and sodium chloride, and it is preferable to use 20 to 100 mg / L. The surfactant is preferably used in an amount of 1 to 20 mL / L, and the brightener is preferably used in an amount of 0.1 to 10 mL / L. It is also possible to use high molecular polysaccharides and low molecular weight glues as chemicals instead of surfactants. Preferably, the surfactant is an essential component, and more preferably includes a brightening agent.

As the surfactant, an anionic, cationic, nonionic or amphoteric surfactant can be used. Nonionic surfactants are particularly preferable.
The nonionic surfactant is a concept that includes a polymeric surfactant, and includes, for example, polymeric surfactants such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, carboxymethyl cellulose, and polyacrylamide. In addition, such polymer surfactants include alkanols having 1 to 20 carbon atoms, phenols, naphthols, bisphenol compounds, alkylphenols having 1 to 25 carbons, arylalkylphenols, and alkyls having 1 to 25 carbons. Alkyl naphthol having, alkoxylated phosphoric acid (salt) having alkyl having 1 to 25 carbon atoms, sorbitan ester, styrenated phenol, polyalkylene glycol, aliphatic amine having 1 to 22 carbon atoms, aliphatic having 1 to 22 carbon atoms An amide or the like may be obtained by addition-condensation of 2 to 300 moles of ethylene oxide or propylene oxide, or both.
Examples of cationic surfactants include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, Examples include trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, and octadecylamine acetate.
Anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, (mono-, di- or tri-) alkyl naphthalene sulfonates, etc. Is mentioned. Examples of the alkyl sulfate include sodium lauryl sulfate and sodium oleyl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include sodium polyoxyethylene nonyl ether sulfate and sodium polyoxyethylene dodecyl ether sulfate. Examples of the polyoxyethylene alkylphenyl ether sulfate include polyoxyethylene nonylphenyl ether sulfate. Examples of the alkyl benzene sulfonate include sodium dodecylbenzene sulfonate. Examples of the (mono, di, tri) alkyl naphthalene sulfonate include sodium dibutyl naphthalene sulfonate.
Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Further, sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
As the brightener, an organic sulfur compound or the like is used.
Examples of the organic sulfur compound include bis (3-sulfopropyl) disulfide, bis (2-sulfopropyl) disulfide, bis (3-sulfo-2-hydroxypropyl) disulfide, bis (4-sulfobutyl) disulfide, and bis (p -Sulfophenyl) disulfide, 3-mercapto-1-propanesulfonic acid, di-n-propyl-thioether-di-3-sulfonic acid, 3- (benzothiazolyl-2-thio) propylsulfonic acid, N, N-dimethyl- Dithiocarbamic acid- (3-sulfopropyl) ester, O-ethyl-diethyl carbonate-S- (3-sulfopropyl) ester, thiourea and its derivatives, S- (2-ethylamido) -thiopropanesulfonic acid, S- ( 3-propylamide) -thiopropanesulfonic acid, S- (4-butylamino) ) -Thiopropanesulfonic acid, S- (3-butylamido) -thiopropanesulfonic acid, S- (3-propylamido) -thiopropyl-2-hydroxy-3-sulfonic acid, S- (3-propylamido) -thio Phenylsulfonic acid, S- (N, N-dimethyl-3-propylamide) -thiopropanesulfonic acid, S- (N-phenyl-3-propylamide) -thiopropanesulfonic acid, and the like, and their sodium and potassium salts There is salt.
In the present invention, the production of a patterned copper metal layer whose surface has been blackened (metal pattern preparation step) includes a conductive layer forming step and a blackening treatment step, and these steps are performed in the same plating bath. In the conductive layer forming step, electrolytic plating is performed on the conductive substrate under a first current density applied between the conductive substrate (cathode) immersed in the electrolytic solution and the anode (ie, Then, copper is deposited in the concave portion (plating forming portion) of the conductive base material), and a conductive copper metal layer is formed.
The volume resistivity of the copper layer is preferably 10 μΩ / cm or less, more preferably 5 μΩ / cm or less. The range of the first current density is not more than the maximum current density indicating the upper limit of the current density for generating a normal film, and more than the critical current density which is the lower limit for generating a normal film. Specifically, the first current density is affected by the composition of the electrolyte, the type and concentration of the additive, and further by the circulation method, temperature, stirring method, and the like, and also by the pattern of the recesses. In general, it cannot be defined, but is preferably determined as appropriate in the range of 0.5 A / dm ² or more and 60 A / dm ² or less. The reason is that a normal film cannot be obtained if the critical current density is exceeded. If it is less than 0.5 A / dm ² , it takes a long time to deposit to the target thickness. As a result, the production efficiency does not decrease and the production cost does not decrease, and if it exceeds 60 A / dm ² , the deposited copper does not become a normal film. It interferes with subsequent processes such as transcription. From this viewpoint, the first current density is preferably 40 A / dm ² or less.
When a conductive substrate having a concave pattern is used as the pattern-like plating forming portion, a smaller current density is preferable in order to form a conductive layer with good quality in the conductive layer forming step, but the plating rate is increased. For this purpose, it is preferable that the current density is large. In this case, it is preferable to adjust the flow and temperature of the plating solution so that a high-quality conductive layer is formed.
The first current density is preferably 0.5 A / dm ² or more and 20 A / dm ² or less.

After the conductive layer forming process, a blackening process is performed. In the blackening treatment step, the blackening treatment is performed on the surface of the copper layer formed in the conductive layer formation step under the second current density applied between the conductive substrate (cathode) and the anode. The The range of the second current density is equal to or higher than the maximum current density indicating the upper limit of the current density for generating a normal film, and the current replenishment of ions by diffusion reaches the limit, and the current density does not increase even when the voltage is increased. It is preferable that the density is not more than the limit current density indicating the maximum density. The appropriate value of the second current density varies depending on the mesh shape and other plating conditions, and thus cannot be generally specified, but is appropriately determined in consideration of the blackness. In some cases, even when the second current density is 1 A / dm ² or 10 A / dm ² , the blackening process can be performed. In general, a finer pattern tends to require a larger current density. If the other conditions are the same, the second current density is generally appropriately selected from a range larger than the selected first current density. If the second current density is too large, the deposited copper tends to form needle-like precipitates and cause defects such as transfer failure and powder falling. For this reason, the upper limit of the second current density is preferably set to 100 A / dm ² .

  The second current density is not limited to one, and two or more may be changed stepwise to control the size of particles deposited as a blackened film.

  In the blackening treatment process, fine copper metal is deposited by electrolytic plating on the surface of the copper metal layer formed in the conductive layer forming process, and thereby becomes black or brownish. This black color appears as a result of the deposition of finely divided copper metal on the copper metal layer formed in the conductive layer forming step underneath, and such fine particles appear on the copper metal layer. It can be said that a black or brown metal layer is formed by overlapping in some cases.

  In order to quantitatively evaluate colors, numerical values are required, and several methods have been standardized by the International Commission on Illumination (CIE). Among them, L * a * There is a b * color system. In this case, L * represents lightness, a * represents reddish green, and b * represents yellowish blue hue and saturation. L * is 0 for perfect black (total absorption of light) and 100 for perfect white (total reflection of light).

Electromagnetic wave shielding material used for the display surface of the display, a substrate with a conductor layer pattern for a transparent antenna or the like is required to have good light transmittance, and therefore it is preferable to reduce the coverage by the conductor layer pattern as much as possible, Further, in order to enhance the image quality by reflecting the brightness of transmitted light without reflecting external light, the conductor layer pattern itself is desirably black. However, since the base material with a conductor layer pattern itself has high light transmittance, it is difficult to directly measure the chromaticity (brightness) of the fine conductor layer pattern itself.
Therefore, when the aperture ratio is about 50%, the brightness of the conductor layer pattern portion is measured against a black background of brightness 25. Specifically, the blackened surface of the conductor layer pattern is raised, a black paper with a brightness of 25 is laid under the conductor layer patterned base material, and the brightness is measured. If the conductive layer pattern is good black, the lightness L * is a value of 25 to 50, and the chromaticities a * and b * are both 5 or less. In the blackening process, it is preferable to adjust the blackness in this way. On the other hand, when the degree of blackening is insufficient and the original color of copper remains, the lightness L * indicates a high value of 60 or more, and both the chromaticities a * and b * are values greater than 5 indicating redness or yellow. It becomes.
In addition, when the aperture ratio increases, it is difficult to measure the blackness with the lightness by the above method, and therefore, it is determined by the chromaticity a * and b *. This method is effective even with an aperture ratio of 50%. That is, when the aperture ratio is 40% or more, the chromaticity of the conductor layer pattern portion is measured against a black background having a brightness of 25 as described above, and both the chromaticities a * and b * are 3 or less, preferably 2 or less. When the value is shown, the conductor layer pattern shows a good black color. In this case, if the mesh-like conductor layer pattern has an aperture ratio of 50% or more, the conductor layer pattern exhibits a good black color and is suitable for use as an electromagnetic shielding material. In the electromagnetic wave shielding material application, it is more preferable that the aperture ratio of the light transmission part is 80% or more.

  The chromaticity can be measured by using a spectrocolorimeter CM-508d (Konica Minolta Holdings) and setting the reflection mode. The colorimetric object part for measuring the brightness and chromaticity of this measuring device is a circle having a diameter of 8 mm, and the average color of the opening can be obtained.

In the conductive layer forming step, it is preferable to deposit the copper metal so that the thickness of the copper metal is 0.1 to 20 μm. In order to exhibit sufficient conductivity (for example, sufficient electromagnetic shielding properties are exhibited or function sufficiently as a current collector of a capacitor), it is preferably 0.1 μm or more, and pinholes are formed in the copper metal layer. In order to reduce the possibility of being formed (in this case, for example, the electromagnetic wave shielding property or conductivity is lowered), the thickness is more preferably 3 μm or more. Also, if the plating thickness is too large, the deposited metal spreads in the width direction, so the width of the transferred line becomes wider, the aperture ratio of the pattern base material with the conductor layer decreases, and transparency and invisibility are reduced. descend. Therefore, in order to ensure transparency and invisibility, the thickness of the deposited metal is preferably 20 μm or less. Further, in order to shorten the plating deposition time and increase the production efficiency, the thickness of the plating is preferred. Is more preferably 10 μm or less.
The blackening process is performed with the lightness or chromaticity described above as a guide. If the blackening process proceeds too much, powder is likely to fall off in the thin line portion, so care must be taken.

In order to peel the plating film satisfactorily without disconnection or peeling failure through the adhesive or pressure-sensitive adhesive with the peeling substrate, it is preferable to perform the plating so that the metal is deposited by about 1 μm or more higher than the insulating layer.
On the other hand, the thickness of the metal formed by plating from the viewpoint that the recessed portion becomes deeper relative to the thickness of the deposited metal layer, so that the deposited metal layer can be more shaped. Is preferably not more than twice the height of the insulating layer, particularly preferably not more than 1.5 times, and more preferably not more than 1.2 times, 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 at the time of peeling of the conductor layer 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.

  As in the present invention, when the blackening treatment is continuously performed from the formation of the copper metal layer, the water washing treatment and the surface treatment of the conductor layer are unnecessary between the conductor layer forming step and the blackening treatment step. Time can be reduced, costs can be reduced, and environmental impact can be reduced.

  The patterned copper metal whose surface has been blackened by peeling off the patterned copper metal layer whose surface has been blackened, formed on the conductive substrate for plating as described above, by an ordinary method. Obtainable. In this case, a patterned copper metal layer (referred to as a blackened patterned copper layer) whose surface is blackened is used as the base material for peeling. Direct the adhesive to the surface of the conductive substrate for plating, press the peeling substrate, peel it off, transfer the blackened patterned copper layer to the peeling substrate, and then remove the conductive substrate for plating The blackened patterned copper layer can also be peeled off. The blackened patterned copper layer is appropriately obtained by peeling from the peeling substrate.

  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 copper metal layer 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 parallel shape. Quadrilaterals, trapezoids, and other quadrangles, (positive) hexagons, (positive) octagons, (positive) dodecagons, (positive) dodecagons, and other (positive) n-gons (n is an integer greater than or equal to 3), circles Metal foils with through-holes such as ellipses and stars, metal foils with recesses of such shapes, individually separated metal foils of such shapes, etc., conductive substrates for plating after plating In order to make it easy to peel off, it is preferable that the foil is a continuous foil 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 copper foil which is an example of a patterned copper metal layer. 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 copper metal layer is present on the conductive substrate for plating.
A hole 10 penetrates the patterned copper metal layer 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 represents the inner circumference (minimum diameter) and the outer circumference (maximum diameter). is 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 copper metal layer 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, and its bottom surface is The thickness of the insulating layer 3 is higher than the bottom surface of the patterned copper metal layer 9 corresponding to the concave portion which is the plating forming portion.

  FIG. 7 is a cross-sectional view showing another example of the patterned copper metal layer, and shows a state existing on the electroconductive substrate for plating as in FIG. The plating deposited in the recesses on the conductive substrate 2 grows on the insulating layer 3 and has no through-holes, but becomes a patterned copper metal layer 9 having recesses corresponding to the insulating layer 3. By extending the insulating layer 3 in the front and back direction of the paper and reducing the width, fine grooves can be formed in the patterned copper metal layer. 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 copper foil without a groove | channel or a recessed part, said patterned copper metal layer 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 copper metal layers may be stacked in the same direction, and the surface including the last exposed groove can be closed with a suitable material. .

In the present invention, the substrate with a conductor layer pattern is
(B) a step of forming a patterned copper metal layer (conductor layer pattern) whose surface is blackened on the conductive substrate for plating; and (b) metal deposited in the recesses of the conductive substrate. Is produced by a method including a step of transferring the material to another substrate.
The step (a) is as described above. Next, the process (b) will be described.

Examples of the other base material (the base material on which the conductor layer pattern is transferred) include a plate made of glass or plastic, a plastic film, a plastic sheet, and the like. As the glass, glass such as soda glass, non-alkali glass, and tempered glass can be used.
Plastics include polystyrene resin, acrylic resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyetheretherketone Resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, thermoplastic polyester resin such as polyethylene terephthalate resin, cellulose acetate resin, fluororesin, polysulfone resin, polyethersulfone resin, polymethylpentene resin, polyurethane resin, diallyl phthalate Examples thereof include thermoplastic resins such as resins and thermosetting resins. Among plastics, polystyrene resin, acrylic resin, polymethyl methacrylate resin, polycarbonate resin, and polyvinyl chloride resin, which are excellent in transparency, are preferably used. The thickness of another substrate is preferably 0.5 mm to 5 mm from the viewpoint of protection of the display, strength, and handleability.

Another substrate in the present invention is preferably a plastic film. The plastic film includes polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, polystyrene, and EVA, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polysulfone, and polyethersulphate. A film made of a plastic such as phon, polycarbonate, polyamide, polyimide, acrylic resin and the like having a total visible light transmittance of 70% or more is preferable. These can be used as a single layer, but may be used as a multilayer film in which two or more layers are combined. Among the plastic films, a polyethylene terephthalate film or a polycarbonate film is particularly preferable from the viewpoints of transparency, heat resistance, ease of handling, and cost.
Although there is no restriction | limiting in particular in the thickness of the said plastic film, The thing of 1 mm or less is preferable, and when it is too thick, there exists a tendency for visible light transmittance | permeability to fall easily. In consideration of the fact that if the film is too thin, the handleability deteriorates, the thickness of the plastic film is more preferably 5 to 500 μm, and further preferably 50 to 200 μm.
These substrates such as plastic films are preferably transparent (that is, transparent substrates) in order to be used as an electromagnetic wave shielding film for preventing leakage of electromagnetic waves from the front surface of the display.

The surface on which the conductor layer pattern of another substrate is transferred needs to have adhesiveness when transferred. For this purpose, the substrate itself may have the necessary adhesiveness, but it is preferable to laminate an adhesive layer on the transfer surface.
The adhesive layer is preferably one that has adhesiveness at the time of transfer or one that exhibits adhesiveness under heating or pressurization. As the adhesive, a resin having a glass transition temperature of 20 ° C. or lower is preferable, and a resin having a glass transition temperature of 0 ° C. or lower is most preferable. As a material used for the adhesive layer, a thermoplastic resin, a thermosetting resin, a resin that is cured by irradiation with active energy rays, or the like can be used. If it shows adhesiveness when heated, if the temperature at that time is too high, the transparent base material may be deformed such as swell, sag, curl, etc., so irradiation with thermoplastic resin, thermosetting resin, active energy rays It is preferable that the glass transition point of the resin that is cured at 80 ° C. or less. The thermoplastic resin, thermosetting resin, and resin cured by irradiation with active energy rays preferably have a weight average molecular weight of 500 or more. If the molecular weight is less than 500, the cohesive strength of the resin is too low, and the adhesion to the metal may be reduced.

  Typical examples of the thermoplastic resin include the following. For example, natural rubber, polyisoprene, poly-1,2-butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-2-t-butyl-1,3-butadiene, poly-1,3 -Dienes such as butadiene), polyethers such as polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether and polyvinyl butyl ether, polyesters such as polyvinyl acetate and polyvinyl propionate, polyurethane, ethyl cellulose , Polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, polysulfide, phenoxy resin, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, poly-t-butyl Acrylate, poly-3-ethoxypropyl acrylate), polyoxycarbonyl tetramethacrylate, polymethyl acrylate, polyisopropyl methacrylate, polydodecyl methacrylate, polytetradecyl methacrylate, poly-n-propyl methacrylate, poly-3,3,5-trimethyl Poly (meth) acrylic acid esters such as cyclohexyl methacrylate, polyethyl methacrylate, poly-2-nitro-2-methylpropyl methacrylate, poly-1,1-diethylpropyl methacrylate, and polymethyl methacrylate can be used. The monomers constituting these polymers may be used as a copolymer obtained by copolymerization of two or more, if necessary, or may be used by blending two or more of the above polymers or copolymers. .

Examples of the resin curable with active energy rays include materials in which an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or the like is used as a base polymer and a radically polymerizable or cationically polymerizable functional group is added to each. As radically polymerizable functional groups, there are carbon-carbon double bonds such as acrylic group (acryloyl group), methacryl group (methacryloyl group), vinyl group, allyl group, etc., and highly reactive acrylic group (acryloyl group) is suitable. Used for. As the cationically polymerizable functional group, an epoxy group (glycidyl ether group or glycidylamine group) is representative, and a highly reactive alicyclic epoxy group is preferably used. Specific materials include acrylic urethane, epoxy (meth) acrylate, epoxy-modified polybutadiene, epoxy-modified polyester, polybutadiene (meth) acrylate, and acrylic-modified polyester. As the active energy rays, ultraviolet rays, electron beams and the like are used.
When the active energy ray is ultraviolet, photosensitizers or photoinitiators added at the time of ultraviolet curing include known materials such as benzophenone, anthraquinone, benzoin, sulfonium salt, diazonium salt, onium salt, and halonium salt. Can be used. In addition to the above materials, a general-purpose thermoplastic resin may be blended.

  As thermosetting resins, natural rubber, isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, halogenated butyl, acrylonitrile-butadiene rubber, styrene-butadiene rubber, polyisobutene, carboxy rubber, neoprene, polybutadiene and the like as crosslinking agents Sulfur, aniline formaldehyde resin, urea formaldehyde resin, phenol formaldehyde resin, ligrin resin, xylene formaldehyde resin, xylene formaldehyde resin, melamine formaldehyde resin, epoxy resin, urea resin, aniline resin, melamine resin, phenol resin, formalin resin, metal oxide Products, metal chlorides, oximes, alkylphenol resins and the like. In addition, for these purposes, additives such as general-purpose vulcanization accelerators can be used for the purpose of increasing the crosslinking reaction rate.

  As a thermosetting resin, those using a curing agent include a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an unsaturated hydrocarbon group, an epoxy group, a hydroxyl group, an amino group, an amide group, Some are used in combination with a curing agent having a functional group such as a carboxyl group or a thiol group, or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide, or peroxide. In addition, for the purpose of increasing the curing reaction rate, additives such as general-purpose catalysts can be used. Specific examples include curable acrylic resin compositions, unsaturated polyester resin compositions, diallyl phthalate resins, epoxy resin compositions, polyurethane resin compositions, and the like.

Furthermore, as a thermosetting resin or a resin curable with an active energy ray, an adduct of acrylic acid or methacrylic acid can be exemplified as a preferable one.
As an adduct of acrylic acid or methacrylic acid, epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1) .49), polyester acrylate (n = 1.48 to 1.54), and the like can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, diglycidyl adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule, such as epoxy acrylate, is effective in improving adhesion. These copolymer resins can be used in combination of two or more as required.

  In the present invention, those having adhesiveness or those exhibiting adhesiveness (hereinafter referred to as “adhesive”) are optionally cross-linking agent, curing agent, diluent, plasticizer, oxidation You may mix | blend additives, such as an inhibitor, a filler, a coloring agent, a ultraviolet absorber, and a tackifier.

If the thickness of the pressure-sensitive adhesive layer is too thin, sufficient strength cannot be obtained. Therefore, when transferring a metal layer formed by plating, the metal does not adhere to the pressure-sensitive adhesive layer, and transfer failure may occur. Accordingly, the thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more, and more preferably 3 μm or more in order to ensure transfer reliability during mass production. Further, if the thickness of the adhesive layer is large, the manufacturing cost of the adhesive layer increases, and the amount of deformation of the adhesive layer increases when laminated, so the thickness of the adhesive layer is preferably 30 μm or less, and more preferably 15 μm or less. preferable.
When a film having a pressure-sensitive adhesive layer formed by applying a pressure-sensitive adhesive to another substrate is bonded to the surface on which the metal layer is formed, the film is heated if necessary according to the characteristics of the pressure-sensitive adhesive.

  When the conductor layer pattern of the substrate with a conductor layer pattern according to the present invention (in the present invention, at least one side is blackened) is used as an electromagnetic wave shielding layer on the front surface of the display, a transparent antenna or the like, the line width is 40 μm or less, and the line interval is preferably 50 μm or more. Further, the line width is more preferably 25 μm or less from the viewpoint of non-visibility of the conductor layer pattern, and the line interval is more preferably 120 μm or more from the viewpoint of visible light transmittance. If the line width is too small and thin, the surface resistance becomes too large and the shielding effect is inferior, so 1 μm or more is preferable. The larger the line spacing, the better the aperture ratio and the visible light transmittance. When the conductor layer pattern obtained by the present invention is used on the front surface of the display, the aperture ratio needs to be 50% or more, more preferably 60% or more, and particularly preferably 80% or more. If the line interval becomes too large, the electromagnetic wave shielding property is deteriorated. Therefore, the line interval is preferably set to 1000 μm (1 mm) or less. When the line interval is complicated by a combination of geometric figures or the like, the area is converted into a square area with the repetition unit as a reference, and the length of one side is set as the line interval. From the viewpoint of visible light transmittance, the line interval is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 120 μm or more. The larger the line spacing, the better the aperture ratio and the visible light transmittance.

  The thickness of the conductor layer pattern (in the present invention, at least one surface is blackened) is preferably 100 μm or less. When applied as an electromagnetic shielding sheet on the front surface of the display, the thinner the thickness, the wider the viewing angle of the display, which is preferable as an electromagnetic shielding material. In addition, the time required to form the metal layer by plating is shortened, so 40 μm or less. More preferably, it is 18 μm or less. If the thickness is too thin, the surface resistance becomes too high and the electromagnetic wave shielding effect becomes inferior. Also, the strength of the conductor layer pattern is inferior, and peeling from the conductive substrate during transfer becomes difficult. And more preferably 1 μm or more.

The example of preparation of the base material with a conductor layer pattern using said electroconductive base material for plating is shown next.
FIG. 8 is a cross-sectional view showing the first half of a production example of a base material with a conductor layer pattern. FIG. 9 is a cross-sectional view showing the latter half.
On the conductive base material 1 for plating, plating is performed in the recesses 4 by the above-described plating step, thereby forming a conductor layer pattern 13 (FIG. 8E). Subsequently, the transfer substrate 14 prepared separately, which is a substrate (transparent substrate) 15, is laminated with an adhesive layer 16. Preparation is made for pressure-bonding the transfer substrate 14 with the adhesive layer 16 facing the conductive substrate 1 for plating on which the conductor layer pattern 13 is formed (FIG. 8F).
Next, the transfer base material 13 is pressure-bonded to the electroconductive base material 1 for plating on which the conductor layer pattern is formed with the adhesive layer 16 facing (FIG. 9G). At this time, the pressure-sensitive adhesive layer 16 may contact the insulating layer 7.
Next, when the transfer base material 14 is peeled off, the conductor layer pattern 13 adheres to the pressure-sensitive adhesive layer 16 and is peeled from the recess 4 of the plating conductive base material 1. Is obtained (FIG. 9 (h)).

FIG. 10 is a cross-sectional view showing a state in which a conductor layer pattern is formed by plating in the recesses of the conductive base material for plating, and FIG. 11 is with a conductor layer pattern obtained by transferring the conductor layer pattern in the recesses. Sectional drawing of a base material is shown.
Since plating grows isotropically when plating on a conductive substrate for plating, the deposition of plating that started from the exposed portion of the conductive substrate overflows from the recess and covers the insulating layer as it progresses. To protrude and precipitate. From the viewpoint of sticking to the transfer substrate, it is preferable to deposit the plating so as to protrude. However, at this time, the plating may be deposited so as to be contained in the recess 4. This state is shown in FIG. Even in this case, as shown in FIG. 11, the conductor layer pattern 13 is transferred to another substrate (transparent substrate) 15 through the pressure-sensitive adhesive layer 16 by pressure bonding the substrate for transfer, and for plating. The conductor layer pattern 13 can be peeled from the conductive substrate 1 to produce a substrate 17 with a conductor layer pattern.

The conductor layer pattern of the substrate with a conductor layer pattern obtained by the present invention can be further blackened to obtain a substrate with a conductor layer pattern having a conductor layer pattern with both sides blackened. For this purpose, there is a method of blackening the conductor layer pattern 13 of the substrate 17 with the conductor layer pattern as shown in FIG. 9 (h) or FIG.
When a substrate with a conductor layer pattern having a blackened conductor layer pattern is used on the front of the display as an electromagnetic wave shielding member, generally, the surface on which the black layer is provided faces the viewer side of the display. However, if the substrate has a conductor layer pattern that has a conductor layer pattern that has been blackened on both sides, the blackened surface will face the viewer side on either side. Therefore, the range of product design as an electromagnetic wave shielding member is expanded.

  The above blackening treatment method is a method of forming a black layer on a metal pattern. For this purpose, various methods such as plating, oxidation treatment, and printing can be used for the metal layer.

  As the blackening treatment when the blackening treatment step is performed after transferring to another substrate, it is desirable to perform black plating such as black nickel plating.

  Black nickel plating is a plating method in which a black alloy containing nickel sulfide as a main component is formed by electrodeposition on the surface of the object to be plated, but it is used because both the Group VIII elements iron and cobalt exhibit a black color. be able to. Among the same Group VIII elements, nickel sulfide exhibits a suitable black color and has good adhesion to the underlying metal. For sulfides other than Group VIII elements, silver, mercury, copper, lead and the like can be used. Further, even if alloy plating such as tin and nickel, tin and cobalt, or black chrome plating is used, there is no powder fall and a blackening treatment layer (black layer) having good adhesion can be formed only on the metal layer.

When forming the black nickel plating layer, a plating solution containing nickel sulfate 60 to 100 g / L, nickel ammonium sulfate 30 to 50 g / L, zinc sulfate 20 to 40 g / L, and sodium thiocyanate 10 to 20 g / L is used. be able to. Using this plating bath, under conditions of pH: 4-7, temperature: 45-55 ° C, current density 0.5-3.0 A / dm ² , stainless steel anode or nickel anode, circulation pump and air stirring for stirring By using this, a black nickel plating layer suitable for a plasma display panel can be formed. As a pretreatment for black nickel plating, it is more preferable to perform appropriate alkali degreasing and acid cleaning in order to improve the adhesion to the metal layer as the base. When plating is performed at a concentration exceeding the concentration range of each component, the plating solution is easily decomposed and it becomes difficult to obtain a good black color. Further, when plating is performed at a temperature exceeding 55 ° C., the plating solution is easily decomposed. On the other hand, when the plating is performed at a temperature of less than 45 ° C., 1.0 A / dm ² or more, the product becomes rough and easily powdered, and the life of the plating solution is shortened. Although it is possible to perform plating at a current density of less than 45 ° C. and a current density of 1.0 A / dm ² or less, long-time plating is required to obtain a desired black color, and productivity is lowered. Therefore, the temperature range when performing black nickel plating in a short time using the plating solution having the above concentration composition is optimally 45 to 55 ° C. The current density can be 0.5 A / dm ² or less within the temperature range, but a long plating time is required to obtain the desired black color. When plating is performed at 3.0 A / dm ² or more, a black coating is formed which is easy to decompose the plating solution and easily fall off. In black nickel plating, when a stainless steel anode is used, the life of the plating solution is shortened. Therefore, it is usually desirable to use a nickel anode.

  When the base material with a conductor layer pattern in the present invention is used as an electromagnetic wave shielding body, it can be used as it is by being attached to a display screen with or without another adhesive as appropriate. You may apply to a display after sticking to. Other substrates need to be transparent for use to block electromagnetic waves from the front of the display.

FIG. 12 shows a cross-sectional view of an electromagnetic wave shielding member obtained by sticking a base material with a conductor layer pattern to another base material. In FIG. 12, a conductor layer pattern 13 made of copper is pasted on an adhesive layer 16 laminated on a base material (another base material) 15, and another base material 18 is laminated thereon. The conductor layer pattern 13 is embedded in the pressure-sensitive adhesive layer 16. This can be produced by pressing the conductor layer pattern 13 side of the substrate with the conductor layer pattern to the other substrate 18 under heating or non-heating. In this case, the conductor layer pattern is embedded in the pressure-sensitive adhesive layer 16 by applying an appropriate pressure while the pressure-sensitive adhesive layer 16 has sufficient fluidity or has sufficient fluidity. As the base material (another base material) 15 and the base material (another base material) 18, an electromagnetic wave shielding member having high transparency can be obtained by using a material having transparency and excellent surface smoothness. Obtainable.
FIG. 13 shows a cross-sectional view of an electromagnetic wave shielding member in which a substrate with a conductor layer pattern is covered with a protective resin. A conductive layer pattern 13 made of metal is attached on an adhesive layer 16 laminated on a base material (another base material) 15, and these are covered with a transparent protective resin 19.

FIG. 14 shows a cross-sectional view of an electromagnetic wave shielding body according to another embodiment. In this electromagnetic wave shielding body, the electromagnetic wave shielding member in FIG. 13 is a surface opposite to the surface on which the conductor layer pattern 13 of the base material 15 is provided, and another base material 21 is bonded through the adhesive layer 20. is there.
FIG. 15 further shows a cross-sectional view of an electromagnetic wave shielding body according to another aspect. In FIG. 14, a conductor layer pattern 13 made of metal is bonded to a base material (another base material) 15 via an adhesive layer 16, and is coated with an adhesive or an adhesive 22 made of a transparent resin. Further, a protective film 23 is laminated thereon. Another substrate 21 such as a glass plate is attached to the other surface of the substrate 15 via an adhesive layer 20. In this electromagnetic wave shielding member, the surface on which the conductor layer pattern 13 of the substrate with the conductor layer pattern having the conductor layer pattern 13 adhered to the substrate (another substrate) 15 via the adhesive 16 is transparent. Then, the protective film 23 is further laminated, and the adhesive is then applied to the other surface (the surface on which nothing is laminated) of the substrate 15 of the obtained laminate. Then, the adhesive layer 16 can be formed and pressed against another substrate 21 to be bonded. As said transparent resin 22, the adhesive agent or adhesive which has as a main component the resin hardened | cured with an active energy ray other than a thermoplastic resin and a thermosetting resin can also be used. It is preferable to use a resin that cures with an active energy ray because it cures instantaneously or in a short period of time, resulting in an increase in productivity.

  In the base material with a conductor layer pattern in the present invention, the aperture ratio of the conductor layer pattern can be increased, thereby making it possible to improve the translucency. The base material with a conductor layer pattern in the present invention can be used as a translucent electromagnetic wave shielding member.

  In addition, when the substrate with a conductor layer pattern in the present invention is used as an electromagnetic wave shielding member on the front surface of a display or the like, the surface of the conductive layer pattern is blackened to ensure visibility including antireflection and the like. It is preferable that The front surface of the electromagnetic wave shielding member is preferably black to dark brown from the viewpoint of achieving high contrast and satisfying requirements such as a black screen when the display is turned off.

  As a rust preventive treatment for the conductor layer pattern whose surface has been blackened, chromate treatment, benzotriazole, or the like can be used as a known means. Commercially available rust preventives can also be used. In addition, it is desirable to perform a rust prevention treatment when the blackening treatment is performed again after the conductive layer whose surface has been blackened is transferred to another substrate. As the antirust treatment, chromate treatment, benzotriazole or the like can be used as a known means. Commercially available rust preventives can also be used. Further, when the blackened layer is formed again by the same method after transferring the conductive layer pattern with the blackened layer to another substrate, it is desirable to perform the rust prevention treatment in the same manner.

  By using the rotating body, the structure can be obtained as a scroll while continuously peeling the pattern formed by electrolytic plating. That is, in FIG. 16, the electrolytic solution (plating solution) 102 in the electrolytic bath 101 is supplied to the space between the anode 103 and the rotating body 104 such as the drum electrode by the pipe 105 and the pump 106. When a voltage is applied between the anode 103 and the rotator 104 and the rotator 104 is rotated at a constant speed, a conductor layer is electrolytically deposited on the surface of the rotator 104. By applying a voltage higher than that between the anode 103 and the rotating body 104 during this period, a black or brown film can be deposited on the deposited conductor layer pattern. The number of anodes 107 is not limited to one, and two or more anodes may be attached, and the size of particles deposited as a blackened film may be controlled by changing the voltage stepwise.

  In the state shown in FIG. 16, the anode 103 for performing the conductive layer forming step for forming the conductive metal layer under the first current density, and the surface of the conductive metal layer under the second current density. Further, the anode 107 for performing the blackening treatment step for depositing the metal so that the surface thereof becomes black or brown is immersed in the plating solution apart from each other. , 107 may be provided with a blocking member 151 made of an insulator. By providing the blocking member 151, it becomes easy to maintain the first current density and the second current density.

  When the conductive substrate is an electric substrate made of a rotating body or a conductive substrate attached to the rotating body, the blocking member 151 is formed in a plate shape and provided between the electrodes 103 and 107. The base end side of the blocking member 151 is integrally fixed to the inner wall of the electrolytic bath 101, and the distal end side of the blocking member 151 is located in the vicinity of the conductive base material (rotating body 104). Therefore, the plating solution communicates between the conductive substrate 104 and the tip of the blocking member 151.

  The material of the anodes 103 and 107 is preferably an insoluble anode in which a thin film of a platinum group metal or its oxide is formed on the surface of a titanium metal base. Further, the shape is not particularly limited, and examples thereof include a flat plate shape, a rod shape, a porous shape, and a mesh shape.

  That is, for example, as shown in FIG. 17, a plurality of anodes 103a (anode corresponding to the anode 103) whose cross section perpendicular to the longitudinal direction is rectangular, and one or a plurality of anodes whose cross section perpendicular to the longitudinal direction is rectangular. The anode 107b (the anode corresponding to the anode 107) may be arranged on the circumference of the rotation center axis CL1 of the rotating body 104.

The conductor layer pattern that has been blackened is adhered to the formed conductor layer pattern 108 while being peeled from the rotating body 104 continuously while the adhesive support 109 is pressed against the formed conductor layer pattern 108 by the pressure contact roll 110. The adhesive support body with a conductive layer pattern 111 can be wound up on a roll, and the conductive layer pattern can be produced in this manner. After the conductor layer pattern is peeled from the rotating rotating body, the surface of the rotating body or the conductive substrate fixed to the rotating body is cleaned with a brush roll before being immersed again in the electrolyte. Also good. Although not shown, a draining roll may be installed at the upper end of the anode in order to prevent the electrolyte circulating at high speed from being ejected upward. The electrolyte stopped by the draining roll returns to the bottom electrolyte bath from outside the anode and is circulated by the pump. Although not shown, it is desirable to add a step of adding a consumed metal ion source, an additive or the like as necessary, and a step of analyzing each component during the circulation.
In the above, the conductor layer pattern is obtained as the adhesive support 111 with the conductor layer pattern. However, without using the adhesive support 109, the conductor layer pattern is separated from the rotating body and collected. You may do it.

  Further, a first anode for performing a conductive layer forming step of forming a conductive metal layer under the first current density, and a surface of the conductive metal layer under the second current density Also serving as a second anode for performing a blackening treatment step for depositing metal so that the surface is black or brown, after the formation of the conductive layer under the first current density, The blackening process may be performed under a second current density.

  In the conductive substrate for plating having a concave pattern as the plating formation portion described in detail above, the concave pattern is produced with an appropriate width.

  When the region is defined as region A, the conductive substrate for plating according to the present invention can be provided with a region (referred to as region B) corresponding to the ground portion of the electromagnetic wave shielding member around it. At this time, the region A and the region B may have the same pattern. Moreover, it is preferable to make the area ratio of the recessed part in the area | region A the same or larger than the area ratio of the recessed part in the area | region B, and it is still more preferable to enlarge 10% or more. The area ratio of the recesses refers to the ratio of the area of the part excluding the exposed part in the convex part of each area to the total area of each area when viewed in a plan view. In addition, in this case, a solid metal film is formed on the periphery of the conductive substrate for plating by plating. Since the solid metal film is easily broken during transfer, the area ratio of the recesses in the region B is preferably 40% or more, and preferably less than 97%.

In the region B, the geometric diagram shape drawn by the pattern of the recesses can be the one described above.
(1) Mesh-like geometric pattern (2) Square geometric pattern regularly arranged at predetermined intervals (3) Parallelogram pattern regularly arranged at predetermined intervals (4) Circular pattern or ellipse Pattern (5) Triangular pattern (6) Polygonal pattern of pentagon or more (7) Star pattern etc.

  In addition, the formation of the insulating layer and the recesses in the region B can be performed in the same manner as in the region A described above.

  In this invention, it is preferable to use the outer side of a translucent electromagnetic wave shield part as an earth part. This earth part may have the same pattern as the translucent electromagnetic wave shield part, or may have a different pattern. Further, the ground portion may be a pattern as described above or a completely solid film. It is preferable that the ground part is electrically connected to the inner translucent electromagnetic wave shield part.

  When the part corresponding to the conductor layer pattern of the light-transmitting electromagnetic wave shield part of the conductive base material for plating is a rectangular body or a rotating body, it corresponds to the conductor layer pattern of the light-transmitting electromagnetic wave shield part on the outside. A portion (without an insulating layer) having the same height as the upper surface of the convex portion can be provided in a continuous band shape so as to surround the above-mentioned portion or along two opposing pieces. Thereby, the conductor layer pattern metal layer which has the strip | belt-shaped plating foil continuous in the part of the conductor layer pattern can be formed after the plating to a conductive base material. For example, a plan view of the pattern is shown in FIG. In FIG. 18 (a), the black portion is a conductor layer pattern formed by plating and a foil portion continuous therewith. By having this foil part, foil itself becomes a support body and becomes easy to peel a conductor layer pattern from an electroconductive base material. Since the obtained conductor layer pattern can be sufficiently supported at both ends during the subsequent steps, it is excellent in handling. In some cases, peeling can be performed without using an adhesive support. Unnecessary portions of the foil portion can be cut off later, and the foil portion can be used as a grounding portion with a certain width. Another example of the pattern is shown in FIG. This is a plan view of a part of the conductor layer pattern metal layer that can be produced when a rotating body is used as the conductive substrate, or when a conductive support is attached to the rotating body. Thereby, a ground part can be formed in the four sides of the translucent electromagnetic wave shield part. In the conductor layer pattern obtained in the present invention, when an electromagnetic wave shielding member is produced, a band-like conductor layer (frame portion) is in a conductive state around the mesh-like conductor layer pattern in order to ground the shielded electromagnetic wave as a current. A continuous pattern is more preferable.

In the present invention, the conductor layer pattern produced on the conductive substrate for plating is transferred from the conductive support using an intermediate adhesive support by the same transfer method as described above. Further, the conductor layer pattern may be transferred from the intermediate adhesive support to the final adhesive support in the same manner as in the transfer method. In addition, an electromagnetic wave shielding body can be produced by stacking and pressing an intermediate adhesive support having a transferred conductor layer pattern and a final adhesive support with the conductor layer pattern interposed therebetween. Examples of the pressure bonding method in this case include a method of pressurizing with a press machine at room temperature or under heating, a method of passing between pressure rolls at room temperature or under heating, and the like.
When the base material with a conductor layer pattern in the present invention is used as a shield, an antireflection layer, a near infrared shielding layer, or the like may be further laminated. The base material itself that transfers the metal deposited on the electroconductive base for plating may also serve as functional layers such as an antireflection layer and a near infrared shielding layer. Furthermore, the cover film used when the conductor layer pattern layer is coated with a resin may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.

  In addition to the electromagnetic wave shielding member, the substrate with a conductor layer pattern includes a touch panel member, solar cell electrode extraction or wiring, digitizer member, skimming barrier card member, transparent antenna, transparent electrode, opaque electrode, electronic paper member, adjustment paper, and the like. It can be applied as an optical film member.

(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 line width of the light transmission part is 15 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square). Then, the negative film in which the pattern was formed in a lattice shape with a size of 120 mm square was left on one side of the 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% sodium carbonate aqueous solution, a lattice pattern made of a resist film having a line width of 16 to 19 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was formed on the SUS plate. The width (d ₀ ) of the contact portion of the protrusion with the conductive substrate was 0 to about 1 μm smaller than this maximum width. Further, the minimum width of the protrusion is 0 to about 2 μm smaller than the maximum width (d ₁ ), and is a width at a slightly higher position from 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 convex pattern is formed is exposed, it is not developed and a resist film is formed on the entire surface (corresponding to FIG. 3B).

(Formation of insulating layer)
A DLC film is formed by a PBII / D apparatus (Type III, manufactured by Kurita Manufacturing Co., Ltd.). A stainless steel substrate with a resist film attached thereto was placed in the chamber, the inside of the chamber was evacuated, and 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. Next, toluene, methane, and acetylene gas were introduced, and a DLC layer was formed on the intermediate layer so as to have a film thickness of 2 μm (corresponding to FIG. 3C). At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 2 μm. The angle of the boundary surface was 45 to 51 degrees. In addition, the thickness of the insulating layer and the angle of the boundary surface were measured by cutting a part of the conductive base material and casting it with resin, and observing the cross section with SEM at 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.

(Concavity formation; removal of convex pattern with insulating layer attached)
The stainless steel substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern 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 (corresponding to FIG. 3D).
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 2 μm. Moreover, the width | variety in the bottom part of a recessed part was 16-19 micrometers, and the width | variety (maximum width) in an opening part was 21-27 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface on which the pattern of the conductive substrate for plating obtained above was not formed. Electrolytic copper plating was performed using the conductive substrate for plating with the adhesive film attached as a cathode. The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.
Concentration of copper sulfate (pentahydrate): 200 g / L
Concentration of sulfuric acid: 100 g / L
Hydrochloric acid (35%) consumption: 0.2 mL / L
Additive: Microfil VF-AN (Meltex, organic sulfur compound, bis (3-sulfopropyl) disulfide salt)) 0.3 mL / L
Microfil VF-BN (Meltex, surfactant, polyethylene glycols containing 1 to 4 quaternary ammonium groups) 15 mL / L
Bath temperature: 25 ° C
Anode: Copper plate The plating bath was aerated so that the solution was sufficiently stirred. On the metal surface of the concave portion of the conductive substrate, plating was performed at a current density of 10 A / dm ² until the thickness of the deposited metal reached 4 μm. The deposited metal at this stage was red, and the conductivity was 0.05Ω / □. Thereafter, the aeration was stopped to eliminate the liquid stirring, the current density was changed to 50 A / dm ^2, and plating was continued for 5 seconds to blacken the surface. The conductive substrate with the conductive pattern whose surface was blackened was taken out of the plating bath, washed with water, and dried.

(Preparation of adhesive film for transfer)
On the surface of a polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm, a primer (HP-1, manufactured by Hitachi Chemical Co., Ltd.) is 1 μm in thickness), and an acrylic polymer ( HTR-280 (manufactured by Nagase Chemtech Co., Ltd.) was sequentially applied to a thickness of 10 μm to prepare an adhesive film for transfer.

(Transcription)
The surface of the pressure-sensitive adhesive layer of the transfer pressure-sensitive adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern whose line width is 20-25 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness is 5 micrometers on average was obtained. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.
As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off. The line width and conductor layer thickness were measured by partially cutting out the obtained base material with a conductor layer pattern and casting it with a resin, and observing the cross section with a magnification of 3000 times by SEM. Since the measurement points were 5 and both sides of the recess were measured, the maximum and minimum values of 10 points in total were adopted (the same applies below). The line pitch was measured using a microscope (digital microscope VHX-500, manufactured by Keyence Corporation) at a magnification of 200 times, and the measurement was performed at five random points (the same applies to the following). ).

(Formation of protective film)
The surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV curable resin HITAROID 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film (macro hole DE, Bayer Co., Ltd.). And the conductor layer pattern is embedded in the UV curable resin and then irradiated with 1 J / cm ² of ultraviolet rays using an ultraviolet lamp to cure the UV curable resin to form a protective film. The base material with a conductor layer pattern was obtained.

(Repeated use)
Next, using the conductive substrate for plating described above, the copper plating transfer process was repeated 500 times in the same manner as described above. As a result, there was no change in the transfer property of the copper plating, and no peeling of the insulating layer was observed. It was.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained substrate with a conductor layer pattern were measured using a spectrocolorimeter CM-508d (manufactured by Konica Minolta Holdings, Inc.). The measurement was performed in a reflection mode by placing black paper having a lightness L * of 25 on the lower side of the substrate.
The measurement target was a conductor layer pattern whose surface was blackened, and the opening area was about 77%. As a result of the measurement, the lightness L * was 43, which was within a preferable value range. Further, the chromaticity was a * of 2.8 and b * of 2.2, both of which were low in hue.

  As a resist film used in forming the convex pattern of Example 1, Photec RY3415 (15 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was used as a conductive substrate, and a titanium plate (# 400 polished finish, thickness 0.5 mm). A substrate with a conductor layer pattern was produced in the same manner as in Example 1 except that Micron Industry Co., Ltd. was used. The obtained base material with a conductor layer pattern was subjected to red and black electroplating in the same manner as in Example 1, and after transfer to the transfer adhesive film in the same manner as in Example 1, a protective film was formed.

  The brightness and chromaticity of the obtained conductor layer pattern were measured in the same manner as in Example 1. The measurement target was a conductor layer pattern whose surface was blackened, and the opening area was about 80%. As a result of the measurement, the lightness L * was 47, which was within a preferable range. The chromaticity was 1.4 for a * and 1.7 for b *, both of which were low in hue.

A substrate with a conductor layer pattern was produced in the same manner as in Example 2 except that the bath composition of the electrolytic copper plating bath was as follows.
Concentration of copper sulfate (pentahydrate): 60 g / L
Concentration of sulfuric acid: 170 g / L
Hydrochloric acid (35%) consumption: 0.2 mL / L
Additive: Kaparaside GS (Atotech, organic sulfur compound) 0.1mL / L
Kaparaside HL (manufactured by Atotech, surfactant) 20mL / L
Bath temperature: 25 ° C
Anode: Titanium-based platinum coating plate

  The brightness and chromaticity of the obtained conductor layer pattern were measured in the same manner as in Example 1. The measurement target was a conductor layer pattern whose surface was blackened, and the opening area was about 80%. As a result of the measurement, the lightness L * was 48, which was within a preferable range. Further, the chromaticity was a * of 1.9 and b * of -1.0, and a low hue value was obtained.

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 copper foil which is an example of a patterned copper metal layer. FIG. 6 is a cross-sectional view taken along the line AA ′ in FIG. 5 (however, it is present on a conductive substrate for plating). Sectional drawing which shows another example of a patterned copper metal layer (however, the state which exists on the electroconductive base material for plating). Sectional drawing which shows the first half of the example of preparation of the base material with a conductor layer pattern. Sectional drawing which shows the second half of the preparation examples of the base material with a conductor layer pattern. Sectional drawing which shows the state which formed the conductor layer pattern by plating in the recessed part of the electroconductive base material for plating. Sectional drawing of the base material with a conductor layer pattern obtained by transferring the conductor layer pattern in the recessed part shown in FIG. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using a rotary body. The conceptual sectional drawing of the modification of the apparatus for producing the base material with a conductor layer pattern continuously using a rotary body. The top view of a conductor layer pattern.

Explanation of symbols

1: Conductive substrate for plating 2: Conductive substrate 3: Insulating layer 4: Recessed portion 5: Photosensitive resist layer (photosensitive resin layer)
6: Protrusion 7: DLC film 8: Intermediate layer 9: Patterned copper metal 10: Hole (through hole)
11: Stepped portion 12: Inclined portion 13: Conductive layer pattern 14: Transfer base material 15: Another base material 16: Adhesive layer 18: Other base material 19: Protective resin 20: Adhesive 21: Other base material 22: Adhesive or adhesive 23: Protective film 101: Electrolytic bath 102: Electrolytic solution 103: Anode 104: Rotating body 105: Piping 106: Pump 107: Anode 108: Conductive layer pattern 109: Adhesive support 110: Pressure contact roll 111: Adhesive support with conductor layer pattern 151: Blocking member

Claims (48)

  In the method of manufacturing a patterned copper metal layer whose surface is blackened using a conductive substrate for plating, the conductive substrate for plating has an insulating layer formed on the surface of the conductive substrate. A conductive substrate for plating in which the insulating layer is wide in the opening direction and has a recess pattern for forming a plating, and a first current is formed in the recess of the conductive substrate for plating. A conductive layer forming step of depositing copper metal under a density to form a copper metal layer, and a surface of the copper metal layer under a second current density larger than the first current density, A method for producing a patterned copper metal layer having a blackened surface, wherein a blackening treatment step of depositing copper metal so as to be black or brown is performed in one copper sulfate plating bath.   2. The surface according to claim 1, wherein the conductive layer forming step is performed in a first electrodeposition region including a first current density, and the blackening treatment step is performed in a second electrodeposition region including a second current density. A method for producing a treated patterned copper metal layer.   In the blackening treatment process, with a background of black having a lightness of 25, copper metal is used so that the light transmission portion having an aperture ratio of 50% has a lightness of 25 to 50, or chromaticity a * and b * are both 5 or less. The manufacturing method of the patterned copper metal layer by which the surface of Claim 1 or 2 made to deposit was blackened.   2. The metal is deposited in the blackening treatment step so that the aperture ratio is 40% or more and the chromaticity a * and b * of the light transmission part are both 2.8 or less with a black background having a brightness of 25 as a background. The manufacturing method of the patterned copper metal layer by which the surface of 2 description was blackened.   In the blackening treatment step, the metal is applied so that the aperture ratio is less than 40% and the chromaticity a * and b * of the light transmitting portion or the light non-transmitting portion with a lightness of 25 as a background is both 5 or less. The manufacturing method of the patterned copper metal layer by which the surface of Claim 1 or 2 made to deposit was blackened.   The method for producing a patterned copper metal layer whose surface is blackened according to claim 1, wherein the copper sulfate plating bath is a copper sulfate plating bath containing a surfactant as an additive. 1st current density is 0.5-40 A / dm < ² >, The manufacturing method of the patterned copper metal layer by which the surface of any one of Claims 1-6 was blackened.   The electroconductive substrate for plating, wherein the concave portion for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself. The manufacturing method of the patterned copper metal layer by which the surface as described in 1 was blackened.   The electroconductive substrate for plating, wherein the insulating layer is made of diamond-like carbon (DLC) or an inorganic material. The production of a patterned copper metal layer whose surface is blackened according to any one of claims 1 to 8. Method. The method for producing a patterned copper metal layer having a blackened surface according to claim 9, wherein the insulating layer is DLC, Al ₂ O ₃ or SiO ₂ in the conductive substrate for plating.   The method for producing a patterned copper metal layer having a blackened surface according to claim 10, wherein the insulating layer is made of DLC having a hardness of 10 to 40 GPa in the conductive base material for plating.   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 manufacturing method of the patterned copper metal layer by which the surface of any one of -11 was blackened.   In the electroconductive base material for plating, the minimum width of a recessed part is 1-40 micrometers, the maximum width of a recessed part is 2-60 micrometers, and the space | interval of a recessed part is 50-1000 micrometers, The surface of any one of Claims 1-12. A method for producing a blackened patterned copper metal layer.   In the electroconductive base material for plating, the angle of a recessed part side surface is 10 to 90 degree with respect to a base material by the side of an insulating layer, The surface of any one of Claims 1-13 was blackened A method for producing a patterned copper metal layer.   In the electroconductive base material for plating, the angle of a recessed part side surface is 10 to 80 degree | times with respect to a base material by the side of an insulating layer, The surface of any one of Claims 1-14 was blackened. A method for producing a patterned copper metal layer.   In the electroconductive base material for plating, the thickness of an insulating layer is 0.5-20 micrometers, The manufacturing method of the patterned copper metal layer by which the surface of any one of Claims 1-15 was blackened .   The method for producing a patterned copper metal layer according to any one of claims 1 to 16, wherein the surface of the conductive substrate is made of steel or Ti in the conductive substrate for plating.   The method for producing a patterned copper metal layer having a blackened surface according to any one of claims 1 to 17, wherein the conductive substrate for plating is a rotating body or a flat plate attached to the rotating body.   As the conductive substrate, a conductive substrate made of a rotating body or a conductive substrate attached to the rotating body is used. A part of the substrate is immersed in a plating solution, and the rotating body is rotated. The manufacturing method of the patterned copper metal by which the surface of any one of Claims 1-17 which performs a transcription | transfer process was blackened.   The patterned copper whose surface according to any one of claims 1 to 19, wherein the copper metal is deposited so that the thickness of the copper metal is 0.1 to 20 µm in the copper metal layer forming step. A method for producing a metal layer.   A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black A second anode for performing a blackening treatment step for depositing a metal so as to become brownish brown is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. 21. The method for producing a patterned copper metal layer having a blackened surface according to any one of claims 1 to 20, wherein a blocked member is provided.   A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black The second anode for performing the blackening treatment step for depositing the metal so as to be brownish brown is also used, and after the formation of the conductive layer formation step under the first current density, the second anode The method for producing a patterned copper metal layer whose surface is blackened according to any one of claims 1 to 19, wherein the blackening treatment step is performed under a current density.   After performing the manufacturing method of the patterned copper metal layer by which the surface was blackened in any one of Claims 1-22, the copper metal layer by which the surface was blackened is peeled from the electroconductive base material for plating A method for producing a patterned copper metal whose surface is blackened. An insulating layer is formed on the surface of the conductive substrate, and a recess is formed on the insulating layer to form a wide plating in the opening direction. A method for producing a substrate with a conductor layer pattern, comprising a metal pattern preparation step of depositing copper metal by plating and a transfer step of transferring the copper metal deposited on the conductive substrate for plating to an adhesive support,
A conductive layer forming step in which a metal pattern forming step forms a copper metal layer under a first current density; and a surface of the copper metal layer under a second current density greater than the first current density. A method for producing a substrate with a conductor layer pattern, wherein a blackening treatment step for depositing a metal so that the surface is black or brown is performed in one copper sulfate plating bath.   25. With a conductor layer pattern according to claim 24, wherein the conductive layer forming step is performed in the second electrodeposition region including the first current density, and the blackening treatment step is performed in the second electrodeposition region including the second current density. A method for producing a substrate.   In the blackening treatment step, copper metal is deposited so that the light transmission portion having an aperture ratio of 50% has a lightness of 25 to 50, or both a * and b * are 5 or less against a black background of lightness 25. The manufacturing method of the base material with a conductor layer pattern of Claim 24 or 25.   25. The blackening treatment step, wherein the metal is deposited so that the aperture ratio is 40% or more and the chromaticity a * and b * of the light transmission part are both 2.8 or less with a black background of 25 lightness as a background. 25. A process for producing a substrate with a conductor layer pattern according to 25.   In the blackening treatment step, the metal is applied so that the aperture ratio is less than 40% and the chromaticity a * and b * of the light transmitting portion or the light non-transmitting portion with a lightness of 25 as a background is both 5 or less. The manufacturing method of the base material with a conductor layer pattern of Claim 24 or 25 made to deposit.   The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 28, wherein the copper sulfate plating bath is a plating bath containing a surfactant as an additive. Method for producing a conductive layer patterned substrate according to any one of claims 24 to 29 the first current density is 0.5~40A / dm ^2.   The base with a conductor layer pattern according to any one of claims 24 to 30, wherein the concave portion for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself. A method of manufacturing the material.   The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 31, wherein the insulating layer is made of diamond-like carbon (DLC) or an inorganic material. Insulating layer, DLC, _Al 2 _{O 3} or the manufacturing method of the conductive layer patterned substrate according to claim 32 is a SiO _2.   The method for producing a substrate with a conductor layer pattern according to claim 33, wherein the insulating layer is made of DLC having a hardness of 10 to 40 GPa.   The 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. The manufacturing method of the base material with a conductor layer pattern of description.   36. The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 35, wherein the minimum width of the recesses is 1 to 40 [mu] m, the maximum width of the recesses is 2 to 60 [mu] m, and the interval between the recesses is 50 to 1000 [mu] m.   37. The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 36, wherein an angle of the side surface of the recess is 10 degrees or more and less than 90 degrees with respect to the substrate on the insulating layer side.   The method for producing a base material with a conductor layer pattern according to claim 37, wherein the angle of the side surface of the concave portion is 30 degrees or more and 80 degrees or less with respect to the base material on the insulating layer side.   The thickness of an insulating layer is 0.5-20 micrometers, The manufacturing method of the base material with a conductor layer pattern of any one of Claims 24-38.   The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 39, wherein the surface of the conductive substrate is made of steel or Ti.   The method for producing a substrate with a conductor layer pattern according to any one of claims 24 to 40, wherein the conductive substrate is a rotating body or a flat plate attached to the rotating body.   As the conductive substrate, a conductive substrate made of a rotating body or a conductive substrate attached to the rotating body is used. A part of the substrate is immersed in a plating solution, and the rotating body is rotated. The manufacturing method of the base material with a conductor layer pattern of any one of Claims 24-41 which performs a transcription | transfer process.   The conductive layer pattern according to any one of claims 24 to 42, wherein, in the conductive layer forming step, the metal is deposited so that the thickness of the metal is 0.1 to 20 µm on the upper surface of the convex portion of the conductive base material. A manufacturing method of a substrate with a mark. In the manufacturing method of the base material with a conductor layer pattern of any one of Claims 24-43,
A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black A second anode for performing a blackening treatment process for depositing a metal so as to be brownish brown is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. The manufacturing method of the base material with a conductor layer pattern characterized by the above-mentioned. In the manufacturing method of the base material with a conductor layer pattern of any one of Claims 24-43,
A first anode for performing a conductive layer forming step of forming a copper metal layer under the first current density; and a surface of the copper metal layer under the second current density is black or black The second anode for performing the blackening treatment step for depositing the metal so as to become brownish brown is also used, and after the formation of the conductive layer under the first current density, the second anode The manufacturing method of the base material with a conductor layer pattern characterized by performing the said blackening process process under an electric current density.   The base material with a conductor layer pattern manufactured by the method of any one of Claims 24-45.   The translucent electromagnetic wave shielding member formed by bonding the surface which has the conductor layer pattern of the base material with a conductor layer pattern of Claim 46 on a transparent substrate.   The translucent electromagnetic wave shielding member formed by coat | covering the conductor layer pattern of the base material with a conductor layer pattern of Claim 46 with resin.

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