JP2008025025A - Method of manufacturing copper metal having blackened surface, method of manufacturing base material with conductive layer pattern, base material with conductive layer pattern and light transmissive electromagnetic wave shielding member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a copper metal layer having a blackened surface. <P>SOLUTION: In the method of manufacturing the copper metal having the blackened surface by depositing copper metal on a conductive base material for plating by plating to blacken the surface, a copper metal layer forming step for depositing copper metal in layer at a first current density and a blackening step for depositing copper metal to have the blackened surface on the surface of the copper metal layer at a second current density larger than the first current density are carried out in one copper pyrophosphate plating bath. The conductive base material for plating can be a conductive base material having a pattern like plated part. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a copper metal whose surface is blackened, a method for producing a substrate with a conductor layer pattern patterned so as to have conductivity and light transmittance, a substrate with a conductor layer pattern, and The present invention relates to a translucent 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.
A plating bath in which two or more anodes are arranged with respect to one drum-like cathode while using the same electrolytic solution as shown in Patent Document 1 by applying the copper foil manufacturing method as described above. After immersing the drum-shaped cathode in half, and rotating it to form a copper foil with the first current density, the second current density is applied to deposit copper on the fine particles on the surface. By doing so, a method for manufacturing a copper foil having a matte surface is known. However, according to the knowledge of the present inventors, it is difficult to blacken the surface by the method of Patent Document 1.

  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. .

  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 transfer method described in Patent Document 2, the step of metal electrodeposition and the step of blackening are separate steps. The solution used in the metal electrodeposition process and the solution used in the blackening process are usually not allowed to mix with each other in the plating tank, and cannot be performed in the same process. 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

An object of the present invention is to provide a method for efficiently producing a copper metal layer or copper metal having a blackened surface.
The present invention also includes a step of electrodepositing and depositing a metal on a pattern on a conductive substrate for plating, and a step of efficiently blackening the surface of the deposited metal, thereby conducting a blackened conductor layer It aims at providing the method of manufacturing a substrate with a pattern with sufficient 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 copper metal manufacturing method in which copper metal is deposited by plating on a conductive base material for plating and the surface of which is blackened, and the surface is blackened, the copper metal is deposited in layers under the first current density And a blackening treatment step of depositing copper metal on the surface of the copper metal layer under a second current density higher than the first current density so that the surface is black. Is performed in one copper pyrophosphate plating bath, a method for producing a copper metal layer having a blackened surface.
2. The copper metal 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. A method for producing a metal layer.
3. 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 3. A method for producing a copper metal layer, wherein the surface according to item 1 or 2 is blackened.
4). In the blackening treatment step, the metal is deposited so that the chromaticity a * and b * of the light transmission part having an aperture ratio of 40% or more are both 2.8 or less against a black background of brightness 25 2. A method for producing a copper metal layer whose surface is 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 copper metal layer by which the surface of claim | item 1 or 2 to be deposited was blackened.
6). Item 6. The surface according to any one of Items 1 to 5, wherein the copper pyrophosphate plating bath is an alloy plating bath containing one or more of Group VI elements such as molybdenum and Group VIII elements such as cobalt and nickel as additives. Method for manufacturing a copper metal layer subjected to chemical treatment.
7). The manufacturing method of the 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). The manufacturing method of the copper metal layer by which the surface of any one of claim | item 1-7 whose electroconductive base material for plating is a conductive base material which has a pattern-shaped plating part was blackened.
9. The manufacturing method of the copper metal layer by which the surface of the claim | item 8 whose electroconductive base material for plating is a conductive base material which has a pattern of a convex part as a pattern-shaped plating part was blackened.
10. The conductive base material for plating is a conductive base material having a geometrical figure-shaped concave portion drawn by a pattern of convex portions, and the surface according to item 9 for depositing copper metal on the tip portion of the convex portion is black. Method for manufacturing a copper metal layer subjected to chemical treatment.
11. The conductive base material for plating is covered with an insulating layer in the concave portion, but the tip portion of the convex portion is exposed, the width of the exposed portion is 1 μm to 40 μm, and an insulating layer is applied to the concave portion. Item 11. The method for producing a copper metal layer having a blackened surface according to Item 10, wherein the height of the subsequent convex portion is 10 μm or more.
12 The manufacturing method of the copper metal layer by which the surface of the claim | item 11 whose surface of the convex part after giving an insulating layer to the recessed part of the electroconductive base material for plating was 10 micrometers or more was blackened.
13. Item 13. The method for producing a copper metal layer having a blackened surface according to Item 11 or 12, wherein the thickness of the insulating layer of the conductive base material for plating is 10 μm or less near the end of the convex side surface.
14 The manufacturing method of the copper metal layer by which the surface of any one of claim | item 7-10 whose space | interval of the convex part of the electroconductive base material for plating is 100 micrometers-1000 micrometers was blackened.
Item 14. The surface according to any one of Items 9 to 13, wherein the insulating layer is formed on the concave surface at a position lower than the position lower by 0.5 to 5 μm than the upper end of the convex portion of the conductive substrate for plating. A method for producing a treated copper metal layer.
15. The manufacturing method of the copper metal layer by which the surface of the claim | item 8 whose electroconductive base material for plating is a conductive base material which has a pattern of a recessed part as a pattern-shaped plating part was blackened.
16. Item 16. The method for producing a copper metal layer having a blackened surface according to any one of Items 1 to 15, wherein the electroconductive substrate for plating is a rotating body or a flat plate attached to the rotating body.
17. 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 Item 16. The method for producing a copper metal having a blackened surface according to any one of Items 1 to 15, wherein the transfer step is performed.
18. The copper metal layer forming step, wherein the copper metal is deposited so that the thickness of the copper metal is 0.1 to 20 μm in the plated portion of the conductive base material, the surface according to any one of items 1 to 17 is black. Method for manufacturing a copper metal layer subjected to chemical treatment.
19. A first anode for performing a copper metal layer forming step of forming a copper metal layer under the first current density; and a surface of the conductive metal layer under the second current density. A second anode for performing a blackening treatment step for depositing metal so as to be black is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. The manufacturing method of the copper metal layer by which the surface as described in any one of claim | item 1-18 characterized by the blackened surface is provided.
20. A first anode for performing a copper metal layer forming step of forming a copper metal layer under the first current density; and a black surface on the surface of the copper metal layer under the second current density And the second anode for performing the blackening treatment step for depositing the metal so that the second current flows after the formation of the conductive layer under the first current density. The method for producing a copper metal layer having a blackened surface according to any one of Items 1 to 18, wherein the blackening treatment step is performed under a density.
21. After performing the manufacturing method of the copper metal layer by which the surface of any one of claim | item 1 -20 was blackened, the copper metal layer by which the surface was blackened is peeled from the electroconductive substrate for plating. A method for producing a copper metal whose surface is blackened.
22. Metal pattern preparation step for depositing copper metal by electroplating on the plating portion of the conductive substrate for plating having a patterned plating portion, and a transfer step for transferring the copper metal deposited on the conductive substrate to the adhesive support In a method for producing a substrate with a conductor layer pattern comprising:
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 the blackening treatment step of depositing metal so that the surface is black is performed in one copper pyrophosphate plating bath.
23. Item 23. The conductive layer patterned base according to Item 22, 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.
24. In the blackening treatment process, the metal is deposited so that the light transmission part having an aperture ratio of 50% has a lightness of 25 to 50, or the chromaticities a * and b * are both 5 or less, with a black background of 25 Item 24. The method for producing a substrate with a conductor layer pattern according to Item 22 or 23.
25. Item 22 or 23 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 against a black background of brightness 25 The manufacturing method of the base material with a conductor layer pattern of description.
26. 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 24. A method for producing a substrate with a conductor layer pattern according to Item 22 or 23.
27. Item 27. The conductor layer pattern according to any one of Items 22 to 26, wherein the copper pyrophosphate plating bath is an alloy plating bath containing one or more of Group VI elements such as molybdenum and Group VIII elements such as cobalt and nickel as additives. A manufacturing method of a substrate with a mark.
28. The manufacturing method of the base material with a conductor layer pattern of any one of claim | item 22-27 whose 1st current density is 0.5-40 A / dm < ² >.
29. Item 29. The method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 28, wherein the electroconductive metal for plating has a pattern of convex portions as a patterned plating portion.
30. Item 29. The conductive layer according to Item 29, wherein the conductive metal for plating is a conductive base material having a convex pattern and a concave portion having a geometrical shape drawn by the convex pattern, and deposits copper metal on a tip portion of the convex portion. A method for producing a patterned substrate.
31. Although the concave portion of the conductive substrate for plating is covered with an insulating layer, the tip portion of the convex portion is exposed, the width of the exposed portion is 1 μm to 40 μm, and the insulating layer is applied to the concave portion. Item 31. The method for producing a substrate with a conductor layer pattern according to Item 29 or 30, wherein the height of the convex portion is 10 μm or more.
32. Item 32. The method for producing a substrate with a conductor layer pattern according to Item 31, wherein the height of the convex portion after applying the insulating layer to the concave portion of the conductive base material for plating is 10 μm or more.
33. Item 33. The method for producing a substrate with a conductor layer pattern according to Item 31 or 32, wherein the thickness of the insulating layer of the conductive substrate for plating is 10 μm or less near the end of the side surface of the convex portion.
34. Item 34. The method for producing a substrate with a conductor layer pattern according to any one of Items 29 to 33, wherein the interval between the convex portions of the conductive substrate for plating is 100 µm to 1000 µm.
35. Item 35. The conductor layer pattern according to any one of items 29 to 34, wherein an insulating layer is formed on the concave surface at a position lower than a position lower by 0.5 to 5 μm than the upper end of the convex portion of the conductive base material for plating. A method for producing a substrate.
36. Item 29. The method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 28, wherein the conductive substrate for plating is a conductive substrate having a concave pattern as a patterned plating portion.
37. Item 37. The method for producing a substrate with a conductor layer pattern according to Item 36, wherein the width of the recess is 1 to 60 µm and the interval between the recesses is 50 to 1000 µm.
38. Item 38. The method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 37, wherein the conductive substrate is a rotating body or a flat plate attached to the rotating body.
39. 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 40. The method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 38, wherein the transfer step is performed.
40. 40. The substrate with a conductor layer pattern according to any one of Items 22 to 39, wherein, in the conductive layer forming step, the metal is deposited so that the thickness of the metal is 0.1 to 20 μm in the plated portion of the conductive substrate. Manufacturing method.
41. Item 41. The method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 40, wherein the metal used for plating contains at least one metal having a volume resistivity of 20 μΩ / cm or less at 20 ° C.
42. In the method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 41,
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. A second anode for performing a blackening treatment step for depositing metal so as to be black 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.
43. In the method for producing a substrate with a conductor layer pattern according to any one of Items 22 to 41,
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. A second anode for performing a blackening treatment step for depositing metal so as to be black 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.
44. Item 44. A substrate with a conductor layer pattern, produced by the method according to any one of Items 22 to 43.
45. Item 45. A translucent 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 44 to a transparent substrate.
46. Item 45. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 44 with a resin.

  According to the present invention, the copper metal layer and the surface blackening treatment can be performed in one plating bath, so that the surface blackened copper metal layer or copper metal can be produced with high productivity. Can do. Thereby, a base material with a conductor layer pattern can also be produced with high productivity.

  When using a conductive substrate for plating whose plating is a patterned convex part and having an insulating layer in the concave part corresponding to the convex part, there is no unnecessary metal plating, and further production in the above method The speed can be improved, and the deposited metal is efficiently peeled off during the transfer in the production of the substrate with the conductor layer pattern. Since the electroconductive base material used for these manufacture can be repeatedly used once produced, a manufacturing process reduces as a whole and production efficiency improves.

  A metal rotating body as a conductive substrate, or a copper metal layer whose surface is continuously blackened by electrically coupling the conductive substrate to a metal rotating body, and its Since the transfer of the metal layer to the adhesive support can be performed, the production efficiency is further improved.

  Further, in the present invention, the metal surface deposited on the tip of the convex portion of the conductive base material is subjected to a blackening process that does not cause powder falling uniformly regardless of the thin wire portion and the wide portion in the metal deposition step and a series of steps. Can do. 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 black metal deposition conditions in the second electrodeposition region, the black metal can be deposited in the form of particles or lumps, 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.

  In this invention, the electroconductive material used for an electroconductive base material has sufficient electroconductivity in order to deposit a metal on the surface by electroplating, and it is especially preferable that it is a metal. In addition, the base material has low adhesion to the metal layer formed on the surface so that the metal layer formed by electroplating 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 conductive substrate for plating in the present invention may have a plated portion on a smooth surface on the above-described conductive substrate so that a solid copper foil can be produced.
Moreover, the conductive base material for plating in the present invention may be a conductive base material having a patterned plating portion. In this case, it is preferable that the portion other than the plated portion is covered with an insulating layer. By using this conductive substrate for plating, a patterned copper metal whose surface is blackened can be produced.

As the conductive substrate having a pattern-shaped plating portion, a conductive substrate having a concave pattern as the pattern-shaped plating portion can be used. At least on the bottom surface of the concave portion, the conductive base material or the conductive material conducting to the conductive base material is exposed so that electroplating is possible.
As a method for producing a patterned plating portion having a concave pattern on a conductive substrate, there is a method of forming a patterned resist film on the conductive substrate.
That is, a geometrical pattern (resist pattern) is formed on a conductive substrate by a photolithographic method or a printing method from a photocurable resin or a thermosetting resin. The remaining resist film functions as an insulating layer, and the conductive substrate is exposed at a portion where unnecessary resist is removed, and this portion becomes a plated portion.
More specifically, (a) a step of forming a photosensitive resist layer on a conductive substrate,
(B) a conductive group having a concave pattern as a patterned plating portion by exposing the photosensitive resist layer through a mask corresponding to the concave pattern and (c) developing the photosensitive resist layer after exposure. A material can be produced.
Also,
(A ′) a step of forming a photosensitive resist layer on a conductive substrate;
(B ') A concave portion is formed as a patterned plating portion by irradiating a portion of the photosensitive resist layer corresponding to the pattern of the concave portion with laser light and (iii) a step of developing the photosensitive resist layer after irradiation with the laser light. A conductive substrate having the pattern can be produced. In this method, a method in which a thermosetting resin is used in place of the photosensitive resist and unnecessary portions are removed by laser light irradiation may be employed.
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 recess) is used as the mask. Further, a positive resist can be used as the photosensitive resist. The portion irradiated with light is appropriately selected according to the type of the photosensitive resist.

  The thickness of the insulating layer is preferably 0.5 μm or more. 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. The thickness of the insulating layer is particularly preferably 1 μm or more. The thickness of the insulating layer relates to the thickness of the plating to be produced, and is appropriately determined according to the purpose. In the case of producing a permeable mesh for an electromagnetic wave shielding material, 10 μm or less is sufficient. When the insulating layer is thick, the time for forming it tends to be long.

As the material of the insulating layer, in addition to the photocurable resin and the thermosetting resin, a carbon thin film similar to diamond, a so-called diamond-like carbon (hereinafter referred to as DLC) thin film having an insulating property. It can also be formed. The DLC thin film is particularly preferable because it is particularly excellent in chemical resistance.
Furthermore, the insulating layer can be formed of an inorganic material such as Al ₂ O ₃ or SiO ₂ .
The method for forming these insulating layers is the same as described later.

The planar shape of the recess or the planar shape of the insulating layer is appropriately determined according to the purpose, but is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square such as a square, a rectangle, a rhombus, a parallelogram, a trapezoid, (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 line width is the same (positive) n-square The larger the n number, the higher the aperture ratio of the conductor layer pattern.

In this invention, the electroconductive base material which has a pattern of a convex part as a pattern-shaped plating part can be used as a conductive base material for plating.
The convex portion of the conductive base material corresponds to the copper metal portion of the patterned copper metal whose surface has been blackened, and similarly corresponds to the conductive layer pattern in the base material with the conductive layer pattern, The conductor layer pattern corresponds to the electromagnetic wave shielding layer when the electromagnetic wave shielding material is finally produced. The planar shape of the convex portion or the concave portion corresponding to the convex shape is a triangle such as a regular triangle, an isosceles triangle or a right triangle, a square such as a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or a (positive) six. Geometric figures such as square, (positive) octagon, (positive) dodecagon, (positive) n-gon (n is an integer greater than or equal to 3), circle, ellipse, star, etc. There may be a pattern in which these are appropriately combined, and these units can be repeated alone or in combination of two or more.

  From the viewpoint of electromagnetic wave shielding, the triangle is most effective. From the viewpoint of visible light transmission, if the number of (positive) n-gons is larger, the aperture ratio of the conductor layer pattern increases with the same line width. From the viewpoint of visible light transmission, the aperture ratio is required to be 50% or more, and the aperture ratio of the conductor layer pattern is more preferably 60% or more. The aperture ratio of the conductor layer pattern is determined from the effective area of the electromagnetic shielding material to the conductive layer from the effective area with respect to the effective area of the electromagnetic shielding material (for example, the area of the range that functions effectively for electromagnetic shielding such as the area where the geometric figure is drawn). It is the percentage of the area ratio minus the area covered.

  FIG. 1 is a perspective view showing an example of a conductive base material on which a geometric figure of a concave portion with respect to a convex portion is formed. The example illustrated in FIG. 1 is a square as a geometrical figure of the concave part 2, and the convex part 3 is formed in a lattice shape on the conductive substrate 1 so that the geometrical figure of the concave part 2 becomes a square. .

  2 and 3 show the AA cross section of FIG. 1, FIG. 2 shows four types (a) to (d), and FIG. 3 shows one type (e). The cross-sectional shapes of the concave portion 2 and the convex portion 3 are appropriately determined, and the side surface 5 of the convex portion 3 is a slope (in the case of (a), (b)), a curved surface (in the case of (c)), a stepped slope ((d ))) Etc. are arbitrary. Also, the bottom surface of the recess 2 has various shapes. In all of these, the side surface of the convex portion has an inclination angle at least at the tip portion. This inclination angle is α in the figure, and preferably corresponds to 30 ° to 80 °, more preferably 50 ° or more.

  The upper surface 4 of the convex portion 3 does not necessarily have to be a flat surface, and the entire upper surface or a part of the upper surface may be deformed from the flat surface. In this case, it is preferable that the upper surface 4 is curved as smoothly as possible. Here, the tip portion of the convex portion means the surface of the convex portion at a position of 0 μm or a low position up to 5 μm from the forefront of the convex portion.

  The reference surface of the angle α is the upper surface of the convex portion, the horizontal surface or the vertical surface. When an original conductive substrate having a (substantially) uniform thickness is used and a convex pattern is applied to this one surface, the other surface can be used as a reference surface. It is also possible to place or fix a sample for cross-sectional observation on a horizontal plane or a vertical plane and observe it. The horizontal plane or the vertical plane can be set using an appropriate table or the like.

  Further, a flat plate that does not bend can be placed on the conductive base material having the convex portion, and the surface of the flat plate can be used as a reference plane. If the conductive base material is a cylinder, prepare a cylinder (reference cylinder) whose cross section is larger than that of the cylinder, place the reference cylinder sideways, and pass these through the conductive base material into the reference cylinder. It is also possible to overlap the cylinders so that the vertices of the cross-sectional circles of the reference cylinder are horizontal, and the tangent surface in contact with the vertices of the cylinder can be used as the reference surface.

  Specifically, the observation of the cross-section of the conductive substrate can be performed with an appropriate magnification of the microscope so that the upper surface of the convex portion can be observed, the other surface (surface) of the conductive substrate can be observed, or , By checking the reference plane so that the reference object can be observed, appropriately increasing the magnification after photography, observing a detailed cross section (cross section with a lower magnification in some cases), and taking a photograph, Measurements regarding the angle α can be made. When checking the reference plane, it is recommended to copy the ruler and other standards at the same time.

  The reference plane described above can also be used as a reference plane for measuring thickness, height and width. Further, in many cases, the surface of another base material is not deformed and is easily adopted as a reference surface.

  On the other hand, as shown in FIG. 3E, the side surface 5 of the convex portion may be a vertical surface.

  The width of the tip portion of the convex portion formed on the conductive base material and the interval between the tip portion of the convex portion are 1 μm to 40 μm in order to make the opening ratio of the conductor layer pattern 50% or more. It is preferable that the center interval (line pitch) of the portions is 100 μm to 1000 μm.

  In the present invention, when the center interval (line pitch) of the tip portion of the convex portion cannot be easily determined because the pattern is a complicated figure or a combination of a plurality of figures, the repeating unit of the pattern is used. As a reference, the area is converted into a square area and defined as the length of one side.

  The height of the convex portion 3 formed on the conductive substrate is defined as the height from the most depressed portion of the concave portion 2 to the tip of the convex portion 3. As for the height of the convex part 3, 11 micrometers or more are preferable. This is because the recess has a sufficient depth even if an insulating layer is formed in the recess. Further, the upper limit of the height of the convex portion 3 is preferably 110 μm. As the height of the convex portion is increased, the aspect ratio increases, so that the processing becomes difficult and the processing cost increases. Therefore, the height of the convex portion is particularly preferably 60 μm or less.

  Examples of the method for forming the convex portion on the conductive substrate include the following methods.

(1) A portion of the conductive base material where the concave portion should be formed (a portion corresponding to the opening of the conductive layer pattern of the base material with the conductive layer pattern) is directly irradiated with laser light to form a concave portion, and the conductive layer pattern A method of forming a convex portion corresponding to
(2) After conducting a step of forming a geometrical pattern (resist pattern) with a photo-curable resin or a thermosetting resin on a conductive substrate by a photolithographic method or a printing method, Etching method,
(3) There is a method of excavating a portion (a portion corresponding to the opening portion of the conductor layer pattern of the substrate with the conductor layer pattern) where the concave portion of the conductive substrate is to be formed by engraving.

  When the material of the conductive substrate is hard, it is preferable to use the method (1) (laser processing method) or the method (2) (etching method) or the like for direct processing. When an excellent material is used, it can be easily processed by the method (3) (engraving method). At this time, after processing, a hard plating such as chrome is applied to the surface to increase the strength. it can.

  In the method (2), when a printing method is used, 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.

  In addition, when using the photolithographic method, a dry film resist or the like is laminated, a mask is attached, exposed, developed, and then a resist film etching process can be performed. After drying or pre-curing, the resist film can be subjected to an etching process after a mask is attached, exposed and developed. If the patterning can be performed by irradiating the photocurable resin with active energy rays through a mask, the mode is not limited. From the viewpoint of productivity, the method of laminating a dry film resist and exposing it through a mask when the size of the plate is large or when it is produced by roll-to-roll (Roll-to-Roll) Preferably, when processing directly on a plating drum or the like, a method in which a dry film resist is bonded or a liquid resist is applied and then directly exposed with a laser or the like without using a mask is preferable.

  The etching of the conductive substrate in the method (2) can be performed using an etching solution. There are various types of etching liquids depending on the material of the conductive metal, and since etching liquids are commercially available for the respective metals, they can be used. For example, if the conductive metal is stainless steel, it is common to use ferric chloride, and if it is titanium, a hydrofluoric acid-based etching solution is often used. Regarding the etching of stainless steel, a liquid having a specific gravity of ferric chloride in the range of 40 ° Be (Baume) to 60 ° Be (Baume) is preferably used. If the specific gravity is low, the etching speed is fast, but the side etching becomes large, so the concave portion tends to become shallow. Conversely, if the specific gravity is high, the etching speed is slow, but the side etching is small, and the concave portion tends to be deep. . Therefore, the specific gravity of the etching solution is more preferably 45 ° Be (Baume) to 50 ° Be. Moreover, since etching speed will fall and productivity will fall when etching temperature is low, it is preferable that it is 40 degreeC or more. Furthermore, if the etching temperature exceeds 60 ° C., the corrosiveness of the etching solution increases, so that the equipment investment such as making the etching tank made of titanium increases. Therefore, the etching temperature is preferably 60 ° C. or less.

  The remaining resist can be stripped using a stripping solution or the like after the conductive substrate is etched.

  The formation of the insulating layer in the concave portion of the conductive base material having the convex pattern and the concave portion of the geometrical drawing shape drawn thereby is performed by forming the insulating layer on the entire surface of the conductive base material, The insulating layer formed on the tip portion of the convex portion is removed by general mechanical polishing using a belt sander or the like, and the metal surface of the tip portion of the convex portion is exposed.

  FIG. 4 is a cross-sectional view of a conductive base material having a convex pattern and a geometrically shaped concave portion drawn thereby, with an insulating layer formed in the concave portion. In FIG. 4, the electroconductive base material which has the cross-sectional shape shown in (c) of FIG. 2 is used. In FIG. 4A, the insulating layer 6 is uniformly formed in the concave portion 2 of the conductive substrate 1 having the pattern of the convex portion 3 having the upper surface 4 and the concave portion 2 of the geometrical diagram shape drawn thereby. . However, the insulating layer 6 is formed so as to be flush with the upper surface 4 from the end of the upper surface 4 of the convex portion 3. Thus, it is particularly preferable that the insulating layer 6 does not protrude above the upper surface 4 when the conductive substrate is leveled. As shown in FIG. 4B, the insulating layer 6 may be formed such that the bottom portion of the concave portion 2 is thicker than the side surface portion 5. Further, as shown in FIG. The thickness of the insulating layer 6 may gradually decrease near the end of the upper surface 4, and the thickness of the insulating layer 6 may be zero in the same plane direction as the upper surface 4.

  In addition, in order to extend the life of the convex pattern, when transferring the metal deposited on the exposed portion of the convex part to another base material, the adhesive surface of the other base material and the concave part of the conductive base material are transferred. It is preferable to reduce contact of the formed insulating layer. Therefore, it is preferable that the height of the convex portion after applying the insulating layer is sufficient. The thickness of the insulating layer is preferably in the range of 1 μm to 10 μm. When the insulating layer is too thick, the time for forming the insulating layer becomes long, so that the working efficiency is lowered. In addition, if the insulating layer is too thin, the adhesion between the insulating layer and the conductive substrate is reduced, and pinholes are likely to be generated. Become.

  It is preferable that the electroconductive base material for plating which has a pattern of a convex part as a pattern-shaped plating part in this invention except that the front-end | tip part of a convex part is coat | covered with the insulating layer.

  When plating is performed on the conductive substrate for plating, the plating grows isotropically, and therefore deposits so as to cover the insulating layer in the vicinity of the exposed portion of the convex portion. Plating that covers the insulating layer causes stress to be applied to the insulating layer every time it is peeled and transferred. Therefore, when an insulating layer is formed on the entire surface of the concave portion, the stress applied to the insulating layer during transfer is greatest in the vicinity of the exposed portion of the convex portion. The stress applied to the layer can be reduced, and as a result, the lifetime of the electroconductive substrate for plating in which the concave portion is covered with the insulating layer can be improved. If the tip of the convex part is exposed too little, the effect of improving the life is small, and if it is too large, plating may be deposited deeply on the side surface and transfer defects may occur. It is preferable that it is from the leading edge of the convex part to a position of 0 μm or as low as 5 μm, more preferably from the leading edge of the convex part to a position 0.5 to 5 μm lower, and 0.5 to 3 μm lower. It is particularly preferable that it is up to the position.

  The structure of the conductive substrate for plating having an insulating layer will be described with reference to the drawings. FIG. 5 is a cross-sectional view showing an example of a conductive substrate having a pattern of convex portions and a concave portion of a geometric diagram drawn by the pattern in the present invention. However, the shape of the recess will be described with reference to FIG. In FIG. 5, three forms of (a), (b), and (c) are shown. In any case, the conductive substrate 1 has a concave portion 2 with respect to the convex portion 3. An insulating layer 6 is formed in the concave portion 2, and the insulating layer 6 is formed along the side surface 5 of the convex portion, but is not formed at the tip portion of the convex portion 3, and therefore, the convex portion The tip is exposed.

  In the figure, h ′ is the height of the convex portion described above. h is the height of the convex portion after applying the insulating layer to the concave portion (hereinafter referred to as “insulating height”). t indicates the thickness of the insulating layer. The height h ′ of the convex part is preferably 11 μm to 110 μm, and more preferably 60 μm or less. The insulation height h is preferably 10 to 100 μm, and t is determined such that h ′ is smaller than h, but is preferably 10 μm or less. It is preferable that the thickness is 1 to 10 μm at the end portion. Further, the tip portion of the convex portion is exposed. As for the degree of exposure of the tip portion of the convex portion, the width d is preferably 1 to 40 μm, and the distance (height direction) s from the tip of the convex portion is preferably 0.5 to 5 μm, More preferably, it is 0.5-3 micrometers. Because of this distance s, the stress applied to the insulating layer at the time of peeling can be reduced. The above h ′, d, and t numerical ranges are preferably satisfied in the same manner when s is 0 μm or less than 0.5 μm.

  The insulating layer is preferably a thin film insulating layer, and preferably has a uniform thickness in order to eliminate non-uniformity in strength.

  FIG. 6 is a cross-sectional view showing an example of a conductive substrate having a pattern of convex portions and a concave portion of a geometric diagram drawn by the pattern in the present invention.

  As shown in FIG. 6, even when the side surface of the convex portion is a vertical surface, the insulating layer is applied to the concave portion in the above-described manner, and if the tip portion of the convex portion is exposed, it can be used as a preferred mode. .

  If the insulation height h is too low, the transfer substrate contacts the conductive substrate during transfer and damages the transfer substrate, or the transfer substrate is provided with an adhesive surface on the conductive substrate. Since it becomes easy to come into contact with the layer and a peeling stress is applied to the insulating layer, the insulating layer may peel off when repeatedly used.

FIG. 7 is a cross-sectional view showing an example of the vicinity of the tip portion of the convex portion of the conductive substrate in the present invention. In FIG. 7, the tip portion of the convex portion 3 is exposed, and the side surface 5 is covered with an insulating layer 6. It is preferable that at least the exposed portion of the convex portion 3 does not increase in width as it advances in the tip direction, and as a whole, the width is smaller at the upper portion than at the lower portion of the convex portion. The exposed portion of the convex portion is near the end of the insulating layer, for example, the end of the insulating layer on the side surface of the convex portion (first position) and the inner side in the width direction by an amount corresponding to 10% of the exposed width of the convex portion. The relationship between the distance d _{10 in} the width direction between the first position and the second position with respect to h ₁₀ in the height direction distance from the position of the convex surface (second position) in FIG. _{relationship)} d _{10 / h} 10 width _{d 10} to the height _{h 10} is preferably equivalent to 30 ° to 80 ° at an angle, and more preferably 50 ° or more.

D ₁₀ is

It is preferable that d ₁₀ is 0.839 × h ₁₀ or more.

  In FIG. 7A, the convex portion 3 of the conductive base material is schematically illustrated as having a trapezoidal cross section, but the surface of the convex portion 3 may be uneven as shown in FIG. 7B. . Moreover, although the surface of the insulating layer is schematically illustrated as a combination of planes in (a), it may be a combination of uneven surfaces as shown in (b). In FIG. 7, the vertical direction is emphasized and is shown to be stretched.

  In FIG. 7, the second position is illustrated so as to be positioned on the side surface of the distal end portion. However, the second position may be positioned on the upper surface of the convex portion depending on circumstances.

  When the side surface of the convex portion has an inclination as described above, plating (metal) deposited by electroplating on the exposed portion of the convex portion of the conductive base material for plating is easier than when it is not, It can be peeled off and transfer can be performed smoothly.

  In addition, when plating is performed on the conductive substrate, the plating grows isotropically, so that the plating also deposits when the convex side surface of the conductive substrate is exposed, but during the transfer, When the transfer substrate is peeled after bringing the adhesive surface of the transfer substrate into contact with the plating, if the stress is applied to the plating layer in an oblique direction, the peel will occur if the angle of the convex portion exceeds 80 °. During (transfer), the resistance becomes too large, and transfer failure may occur. From this, the angle of the convex portion is preferably in the range of 30 ° to 80 °, more preferably 50 ° to 80 °.

  As the insulating material for the insulating layer used in the present invention, a material having high adhesion to metal and strong chemical resistance is preferably used. In the step of electroplating or electroless plating, a material strong in both acid resistance and alkali resistance is more preferable because it is immersed in a plating solution. Among such resins, for example, epoxy resins, urea resins, aniline resins, melamine resins, phenol resins, formalin resins, metal oxides, metal chlorides, oximes, alkylphenol resins, etc. are used as thermosetting resins. These are self-curing (a curing catalyst may be used).

  As the thermosetting resin, one using a curing agent can be used. Examples of such a resin include a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an unsaturated hydrocarbon group, and a functional group such as an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Some are used in combination with a curing agent having a 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. Examples of the method for forming the thin film insulating layer include a method in which the resin or composition is applied by brush coating, spray coating, dipping, etc., and then the resin is scraped off with a squeegee or blade and then dried.

  In addition, as an insulating layer, diamond-like carbon (DLC), graphite-like carbon (GLC), titanium nitride and titanium nitride have excellent adhesion to metal conductors, and have excellent insulation and acid / alkali corrosion resistance. A layer formed by applying aluminum, chromium nitride, titanium nitride chromium, titanium carbonitride, titanium carbide, or the like as a base treatment and then glass coating may be used.

  Furthermore, as the insulating material, an electrodeposition paint may be used because of the uniformity of the film, the ease of formation, and the low environmental burden.

  The electrodeposition paint can be used in any known cationic type or anionic type, and here, an example of the electrodeposition paint that can be used is shown.

  Cationic electrodeposition coatings include cathodic deposition type thermosetting electrodeposition coatings prepared by preparing pastes of resins with basic amino groups, neutralizing them with acids, and then making them water-soluble (dispersed in water). Is done. The cationic electrodeposition coating is applied using the conductive substrate (object to be coated) as a cathode.

  Resins having basic amino groups include epoxy groups such as bisphenol type epoxy resins, epoxy group (or glycidyl group) -containing acrylic resins, glycidyl ethers of alkylene glycols, epoxidized polybutadiene, and epoxidized products of novolak phenol resins. Polymers obtained by adding an amine compound to the epoxy group (oxirane ring) of the resin or an unsaturated compound having a basic amino group (for example, dimethylaminoethyl methacrylate, N-vinylpyrazole, N-diethylaminoethyl acrylate, etc.) A reaction product of a glycol component containing a tertiary amino group-containing glycol (for example, N-methyldiethanolamine) as a component of a glycol with a polyisocyanate compound, and further a reaction between an acid anhydride and a diamine compound. There By producing include those obtained by introducing an amino group to the resin. Here, the amine compound described above is a basic amine compound, which is an aliphatic, alicyclic or araliphatic primary or secondary amine, alkanolamine, tertiary amine, quaternary. Examples include amine compounds such as ammonium salts.

  Moreover, a crosslinking agent can be mix | blended with a cationic electrodeposition coating material. As the crosslinking agent, a blocked polyisocyanate compound is well known. However, when the coating film is heated (about 140 ° C. or higher), the blocking agent is dissociated and the isocyanate group is regenerated, and the above-described cationic resin is contained in the cationic resin. It is cured by crosslinking reaction with a reactive group with an isocyanate group such as a hydroxyl group.

  In addition, for cationic electrodeposition paints, pigments (colored pigments, extender pigments, rust preventive pigments, etc. The amount of pigment is preferably 40 parts by weight or less per 100 parts by weight of resin solids), hydrophilic solvent, water, added An agent etc. can be mix | blended as needed.

  The cationic electrodeposition paint is preferably diluted with deionized water or the like so that the solid content concentration is about 5 to 40% by weight, and the pH is preferably adjusted within the range of 5.5 to 8.0. Cationic electrodeposition paints using the cation type electrodeposition paint thus prepared can usually be carried out using the substrate as a cathode under conditions of a bath temperature of 15 to 35 ° C. and a load voltage of 100 to 400V. In general, the baking temperature of the coating film is suitably in the range of 100 to 200 ° C.

  The anionic electrodeposition paint is preferably an anodic deposition electrodeposition paint based on a resin having a carboxyl group, neutralized with a basic compound, and water-solubilized (water-dispersed). Painted with the (coating object) as the anode.

  As resins having carboxyl groups, maleated oil resins obtained by adding maleic anhydride to drying oils (such as linseed oil, dehydrated castor oil, tung oil), and anhydrous in polybutadiene (1,2-type, 1,4-type, etc.) Maleated polybutadiene added with maleic acid, resin obtained by adding maleic anhydride to unsaturated fatty acid ester of epoxy resin, high molecular weight polyhydric alcohol (molecular weight of about 1000 or more, epoxy resin partial ester and styrene-allyl alcohol copolymer) And the like), resins obtained by adding polybasic acids (trimellitic anhydride, maleated fatty acids, maleated oils, etc.), carboxyl group-containing polyester resins (including those modified with fatty acids), carboxyl group-containing acrylic resins , Polymerizable unsaturated monomers containing glycidyl groups or hydroxyl groups and unsaturated fats Examples thereof include resins obtained by adding maleic anhydride or the like to a polymer or copolymer formed using a reaction product with an acid, and the carboxyl group content is generally about 30 to 200 in terms of acid value. A range is suitable.

  Moreover, a crosslinking agent can be mix | blended with an anion type electrodeposition coating material. As a crosslinking agent, low molecular weight melamine resins, such as hexakis methoxymethyl melamine, butoxylated methyl melamine, and ethoxylated methyl melamine, can be used as needed. Furthermore, anionic electrodeposition paints include pigments (colored pigments, extender pigments, rust preventive pigments, etc. The amount of pigment is preferably 40 parts by weight or less per 100 parts by weight of resin solids), hydrophilic solvents, water Additives can be blended as necessary.

  For the anionic electrodeposition coating, it is preferable to adjust the solid content concentration to about 5 to 40% by weight with deionized water or the like, and maintain the pH in the range of 7 to 9 for use in anion electrodeposition coating. Anionic electrodeposition coating can be carried out according to a conventional method, and for example, it can be carried out with the object to be coated as an anode under conditions of a bath temperature of 15 to 35 ° C. and a load voltage of 100 to 350 V. The anion electrodeposition coating film can be cured by heating in the range of 100 to 200 ° C., preferably 140 to 200 ° C. in principle. However, when an air-dried unsaturated fatty acid-modified resin is used, it is dried at room temperature. It can also be made.

  Furthermore, as the insulating layer used in the present invention, the insulating layer has an insulating property among materials mainly composed of carbon, for example, a carbon thin film similar to diamond, so-called diamond-like carbon (hereinafter referred to as a DLC thin film). It can also be made of a material. The DLC thin film is particularly preferable because it can be etched with oxygen plasma and has excellent chemical resistance.

  As a method for forming the DLC thin film, a dry coating method such as a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method such as a plasma CVD method can be adopted. A plasma CVD method using a high frequency capable of controlling the film temperature 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.

  The manufacturing method of the electroconductive base material for plating which has a pattern of a convex part as a pattern-shaped plating part is demonstrated using drawing.

  8 to 10 are cross-sectional views showing an example of a process showing a method for producing a conductive substrate for plating having a pattern of convex portions as a patterned plating portion. In these, it illustrates using the electroconductive base material which has the cross-sectional shape shown in FIG.2 (c).

  First, the photocurable resin layer 7 is formed on both surfaces of the conductive substrate 1 (FIG. 8A). The photocurable resin layer 7 on one surface of the conductive substrate 1 is patterned using a photolithographic method (FIG. 8B). By etching the conductive substrate using the patterned photocurable resin layer 7 as an etching resist, the etched conductive substrate shown in the figure is obtained (FIG. 8C). At this time, the inclination angle of the side surface 5 of the convex portion 3 can be adjusted (at least at the tip portion of the convex portion). The inclination angle can be adjusted by optimizing the specific gravity of the ferric chloride solution, which is an etching solution, and the etching temperature. Next, the etching resist is removed by dipping in an alkaline aqueous solution such as sodium hydroxide or sodium carbonate (FIG. 8D).

  Next, an adhesive film 9 capable of peeling off one surface of the conductive substrate 1 is bonded and protected, and the entire surface of the etched surface is covered with an insulating layer 8 (FIG. 9E). Thereafter, a mask layer 10 for plasma etching is formed on the insulating layer (FIG. 9F).

  Since the insulating layer is not etched at the portion where the mask layer is formed, the mask layer 10 on the insulating layer 8 formed at the tip of the convex portion 3 of the conductive substrate 1 is removed (FIG. 9G )).

This partial removal of the mask layer 10 is removed in consideration of the width of the tip portion exposed by the protrusion 3. When the convex portion has a planar or substantially planar upper surface, it is preferable that the width of the exposed insulating layer be larger than the width of the upper surface (FIG. 9G). Thereby, in the next partial removal of the insulating layer 8, it becomes easy to remove the insulating layer on the side surface portion near the upper surface of the convex portion 3.
In particular, when the mask layer 10 is removed by polishing, the result is as shown in FIG.

  Next, by performing dry etching on the insulating layer, the insulating layer 8 formed at the tip portion of the convex portion 3 can be removed, thereby exposing the tip portion of the convex portion 3 (FIG. 10 ( h)).

  In particular, when plasma etching is performed with oxygen gas, the conductive base material becomes a stopper layer. When the convex portion has a planar or substantially planar upper surface, if the insulating layer in the portion exceeding the width of the upper surface of the convex portion 3 is exposed (FIG. 9G), the insulating layer is dry-etched. The removal extends to the side surface of the convex portion, and as a result, it can be exposed to the side surface of the convex portion ((FIG. 10 (h)). Can be done by output.

  Next, the mask layer 10 formed on the insulating layer 8 in the recess 2 is removed by chemical solution immersion or the like. Thus, an example of the electroconductive base material for plating which concerns on this invention can be produced (FIG.10 (i)).

  Further, when an intermediate layer is provided between the insulating layer made of DLC and the conductive base material, when the intermediate layer is made of an organic material, for example, following the removal of the insulating layer made of DLC with the oxygen plasma described above. The intermediate layer can be removed, and a conductive substrate for plating having a structure similar to that shown in FIG. When the intermediate layer is not a material mainly composed of carbon, it is difficult to etch the intermediate layer by oxygen plasma. In this case, the gas is changed according to the material of the insulating layer and the intermediate layer, or If the thickness of the intermediate layer is about 0.5 μm or less, the intermediate layer formed at the tip of the convex portion is removed without increasing the exposed width of the tip of the convex portion by mechanical polishing with a weak force. Is possible.

  When the intermediate layer is not etched by oxygen plasma when the DLC thin film is dry etched, the intermediate layer can be dry etched by changing the gas or removed by mechanical polishing. Since the intermediate layer is a thin film, it can be removed by light polishing without thickening the line. In addition, when the intermediate layer is conductive, if the plating deposited by energization can be easily peeled off from the intermediate layer, it is not always necessary to remove the intermediate layer. As such, it can be part of a conductive substrate.

  The mask layer in the present invention can be roughly classified into an inorganic mask layer and an organic mask layer.

As the inorganic mask layer, metals such as aluminum (Al), chromium (Cr), nickel (Ni), cobalt (Co), gold (Au), and titanium (Ti) are particularly preferable because of their high resistance to oxygen plasma. Used. These films are formed by thin film forming methods such as sputtering, vacuum deposition, ion beam deposition, CVD, ion plating, electrodeposition, and electroless plating. Among these materials, aluminum (Al) is preferred because it is highly resistant to oxygen plasma, inexpensive, easy to deposit, and soluble in both acidic and basic substances. Used. Since aluminum is conductive, if it is left after dry etching, plating will be deposited on the entire surface of the conductive substrate, so it must be removed. Etching agents for aluminum include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate, etc. as basic substances, and sulfuric acid, persulfuric acid as acidic substances , Phosphoric acid, hydrochloric acid and salts thereof, etc., which are appropriately selected in consideration of the resistance of the insulating layer.
Further, as an inorganic material having resistance to oxygen plasma, when a wet coating method is used, a metal oxide polymer composed of alkali metal, organopolymetal, organoalkoxy metal, alkoxy metal, modified acetylacetonate metal, etc., inorganic A paint containing a filler and a paint made of silicon compound frit called a ceramic coating can be applied by spraying, dispenser, dipping, roll, spin coating or the like with a solvent such as alcohol or water added. Alternatively, a metal fluoride complex can be used as a mask layer on the insulating layer by a liquid layer deposition method (LPD method) or the like. It is also possible to form various metal oxides by dry coating.
As a coating method, it can be produced using a PVD method such as vapor deposition, sputtering or ion plating, a CVD method such as plasma CVD or thermal CVD, or a method such as thermal spraying. Specifically, Al ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ , MgO, SiO, SiO ₂ , SnO ₂ , TaO ₅ , TiO ₂ , WO ₃ , Y ₂ O ₃ , ZnO, ZnO ₂ , ZrO A film such as ₂ is preferably used.

  In addition, the organic mask layer is resistant to dry etching, and a known one can be used. In particular, when oxygen plasma is used, a resist film containing silicon is generally resistant to oxygen plasma. Therefore, it is used favorably. The resist film containing silicon may or may not be photosensitive. As a method of removing the mask layer on the upper surface of the convex portion, when the mask layer on the upper surface of the convex portion is developed and removed and then the developed portion is dry-etched, the resist film has photosensitivity. However, when the mask layer on the upper surface of the convex portion is removed by mechanical polishing, the photosensitivity is not necessarily required. The resist film to be used may be negative or positive, and may be liquid or film. In the case of a liquid, it can be applied by spraying, dispenser, dipping, roll, spin coating or the like, and in the case of a film, it can be heated and laminated so that the resist is embedded in the recess.

  The above-described resist film containing silicon will be described. As the silicon-containing photosensitive composition used for the resist film containing silicon, known ones can be used, but as a typical example of a suitable silicon-containing photosensitive composition, the main chain has silicon atoms, A chemically amplified silicon-containing photosensitive composition using a siloxane polymer containing an acid-decomposable group such as an acetal structure, a tertiary ester structure, or a t-butyloxycarbonyl structure, and a resist composition comprising a novolak resin and naphthoquinone diazide And a silicon-containing photosensitive composition for ultraviolet exposure in which an alkali-soluble ladder type polysiloxane having a silicon atom in the main chain and a silanol structure in the molecule is blended. Vinyl polymers and photoacids having a silicon atom in the side chain and an acid-decomposable group such as an acetal structure, tertiary ester structure, t-butyloxycarbonyl structure, or β-silylethyl ester structure in the side chain A chemically amplified silicon-containing photosensitive composition for far-ultraviolet light exposure comprising a generator, a structure formed by polymerization of a monomer containing a silicon derivative of methyl methacrylate, and silicon in the ester part of an acrylate polymer. And a resist composition having a polymer comprising an acrylic monomer having two trimethylsilyl groups, a silicon-containing monomer, maleic anhydride, and a polymer comprising t-butyl acrylate.

  The method of partially removing the mask layer includes (a) a method of developing and removing the mask layer formed on the upper surface of the convex portion by a photolithographic process using a photosensitive mask layer, and (b) a mask layer. For example, there is a method of mechanically polishing the removed portion. In the method (a), the photosensitive mask layer may be either a positive type or a negative type, and the developer may be the same liquid as a mask layer peeling liquid described later. . In addition, as a method of polishing and removing the mask layer (b), for example, there is a method of polishing while rotating the baffle. As the buff, a commercially available non-woven fabric, ceramic buff, diamond buff or the like can be used.

  The dry etching used in the present invention is a method of introducing a gas into a vacuum vessel, exciting the gas with a high frequency, microwave, etc., generating plasma, generating radicals, ions, radicals generated by plasma, This is etching performed by reacting ions with an object to be etched (insulating layer, intermediate layer), converting the reaction product into a volatile gas, and exhausting the reaction product to the outside through a vacuum exhaust system. In dry etching, reactive ion etching and etching are performed in which high-frequency power is applied to the electrode on which the object is to be etched, and the ions generated from the plasma are accelerated by the negative self-bias voltage to impact the object to be etched. In general, plasma etching is used to etch an object to be etched by radicals generated from plasma without applying a bias. Reactive ion etching includes parallel plate type, magnetron type, dual frequency type, ECR type, helicon type, ICP type, etc., and the etching shape that is often obtained at a low pressure is isotropic. Plasma etching apparatuses include a barrel type, a parallel plate type, and a down flow type, and the pressure used is often high, and the etching shape obtained is isotropic. In the present invention, any of the above methods may be used.

In addition, as a gas composition in dry etching, a gas that can etch the formed insulating layer and is difficult to etch the conductive substrate is appropriately selected. As a typical gas composition, an F atom-containing plasma is generated. , F ₂ , CF ₄ -O ₂ , C ₂ F ₆ -O ₂ , C ₃ F ₈ -O ₂ , SF ₆ -O ₂ , SiF ₄ -O ₂ , NF ₃ , ClF ₃ , and unsaturated species Generate plasma, CF ₄ , C ₂ F ₆ , CHF ₃ , CF ₄ -H ₂ , CH ₄ , and further generate plasma containing Cl · Br atoms, Cl ₂ , CCl ₄ , CF ₃ Cl, Cl _2- CCl ₄ , Br ₂ , O ₂ , O ₂ —Ar, etc. that generate oxygen plasma are used. Since it does not have a global warming action and is not corrosive, a gas composition that generates oxygen plasma is preferable, and it is preferable to select a carbon-based material that can etch an insulating layer with oxygen plasma.

  The mask layer for dry etching of the insulating layer is preferably one having an etching rate in dry etching that is similar to or lower than that of the insulating layer. When the etching rate of the mask layer is higher than the etching rate of the insulating layer in the dry etching, the mask layer must be thickened when the insulating layer is thick, and the thickness varies. In some cases, the insulating layer under the mask layer may be etched. Therefore, it is particularly preferable that the etching rate of the mask layer is 1/2 or less of the etching rate of the insulating layer.

  A conventionally known alkaline aqueous solution can be used as the stripping solution for the organic mask layer. For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium.

  Monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methylethanol Alkanolamines such as amine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; diethylenetriamine, triethylenetetramine, propylenediamine, N, N-diethyl Polyethylene, 1,4-butanediamine, N-ethyl-ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,6-hexanediamine, etc. Alkylene polyamines; aliphatic amines such as 2-ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine and cyclohexylamine; aromatic amines such as benzylamine and diphenylamine; piperazine, N- Water-soluble amines such as cyclic amines such as methyl-piperazine, methyl-piper-methyl-piperazine, methyl-piperazine, and hydroxyethylpiperazine are also preferably used.

A quaternary ammonium hydroxide is also preferably used as the mask layer stripping solution. Specifically, tetramethylammonium hydroxide [= TMAH], tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, trimethylethylammonium hydroxide (2-hydroxyethyl) trimethylammonium hydroxide [= choline], (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, etc. Is exemplified. Of these, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, choline and the like are preferable.
One or more quaternary ammonium hydroxides can be used.

  When an organic alkali agent or a quaternary ammonium hydroxide is used as a mask layer stripping solution, it is usually used in a mixture with a water-soluble organic solvent in order to improve the stripping property of the resist film. . Examples of the water-soluble organic solvent include sulfoxides such as dimethylsulfoxide; sulfones such as dimethylsulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone, tetramethylenesulfone [= sulfolane]; N, N-dimethylformamide, N- Amides such as methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, Lactams such as N-hydroxymethyl-2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3- Imidazolidinones such as diisopropyl-2-imidazolidinone; Tylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl And polyhydric alcohols such as ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and derivatives thereof. Among them, dimethyl sulfoxide, dimethyl imidazolidinone, N-methyl-2-pyrrolidone, diethylene glycol monobutyl ether, sulfolane, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferably used. One or two or more water-soluble organic solvents can be used.

  In FIG. 8C, the conductive base material 1 is etched in the case where the width of the upper surface 4 of the convex portion 3 is the same as the width of the resist pattern, but as shown in FIG. In addition, overetching may be performed so that the width of the upper surface 4 of the protrusion 3 is smaller than the width of the resist pattern. In this case, sufficient over-etching is performed to continuously form an insulating layer, as shown in FIG. 11B, and then the resist pattern is peeled to have an insulating layer as shown in FIG. 11C. A conductive substrate may be produced. In the above, the resist pattern forming method, etching method, insulating layer forming method, residual resist peeling method and the like are the same as described above.

  Thereafter, except for the fact that there is no insulating layer on the upper surface of the convex portion, the target conductive substrate for plating as shown in FIG. 10 (i) can be produced in the same manner as in FIG. 9 (f) and thereafter. it can.

  The conductive substrate for plating described above does not necessarily have an insulating layer. It is sufficient if the metal deposited on the tip portion of the convex portion can be selectively transferred. As such, by reducing the surface roughness of the tip of the convex part and increasing the surface roughness of the other part (corresponding to the part where the insulating layer described above is formed), the plating conductive The metal deposited on the tip portion of the conductive substrate can be selectively transferred. If the surface roughness of the tip of the convex part is low and the surface roughness of the other part is rough, the metal appearing in the part other than the tip part (in the recess) becomes granular and tends to deposit discontinuously. Therefore, it is possible to selectively transfer only the metal layer formed on the tip portion of the convex portion by another base material. Specifically, the surface roughness of the tip portion of the convex part is preferably 2.0 μm or less in terms of ten-point average roughness Rz (measured in accordance with JIS B 0601-1994), and Rz is 1. More preferably, it is 0 μm or less. Moreover, as for the surface roughness in a recessed part, it is preferable that Rz exceeds 2.0 micrometers, and it is more preferable that Rz is 3.0 micrometers or more.

  Although a rotating body can be used as the conductive substrate used in the present invention, a roll-shaped rotating body made of a metal that can conduct electricity is desirable as the substrate. Further, it is preferable to use a drum electrode or the like used in the drum type electrolytic deposition method as the rotating body. Of course, even if the conductive base material in which the geometrical concave portion is formed with respect to the convex portion shown above is a flat plate, it can be used by being fixed to the drum so as to electrically conduct it. . When the conductive base material is a flat plate, a single conductor layer pattern product can be produced by a single wafer method. However, when a rotating body is used, the product can be obtained continuously as a scroll. Excellent in productivity.

  As a plating bath used for electroplating in the present invention, a copper pyrophosphate bath is used. The copper pyrophosphate bath is an electrolytic solution containing copper pyrophosphate and pyrophosphate. Specific examples thereof include those having the following composition.

Copper pyrophosphate 63-105 g / L (23-38 g / L as copper content)
Potassium pyrophosphate 200-470 g / L
Including, if necessary,
Ammonia water (specific gravity 0.88) 1-6 mL / L
Potassium nitrate 8-16 g / L
Brightener (mercaptothiazole, mercaptothiazole-based additive, etc.) An aqueous solution in which an appropriate amount is dissolved and blended is used. In addition, sodium pyrophosphate and a commercially available additive for copper pyrophosphate plating can also be used. Furthermore, when one or more components of Group VI elements such as molybdenum and Group VIII elements such as cobalt and nickel are added to the plating bath, the blackening treatment can be performed more stably.

In the present invention, the plating step (referred to as a metal pattern layer forming step when producing a metal pattern) 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, electroplating is performed on the conductive substrate under the first current density applied between the conductive substrate (cathode) and the anode (that is, the convexity of the conductive substrate). Copper is deposited on the front of the part) to form a conductive copper layer.
The volume resistivity of the conductive metal layer conductor layer is preferably 10 μΩ / cm or less, and 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 electrolytic solution, the type and concentration of the additive, the circulation method, the temperature, the stirring method, and the like, and the shape of the conductive substrate for plating ( However, it is preferably determined in the range of 0.5 A / dm ² or more and 40 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 will take a long time to deposit to the target thickness, resulting in a decrease in production efficiency and production cost, and if it exceeds 40 A / dm ² , the deposited copper will not become a normal film. It interferes with subsequent processes such as transcription. From this point of view, the first current density is preferably 35 A / dm ² or less.
When there is no conductive base material having a concave pattern or pattern-shaped plating part as the pattern-like plating part, and a conductive base material that is plated over a large area or the entire surface is used, the conductive layer is of good quality in the conductive layer forming step. A low current density is preferable for forming, but a high current density is preferable for increasing the plating speed. In this case, a high-quality conductive layer is formed by adjusting the flow and temperature of the plating solution. It is preferable to adjust so that. In these cases, the first current density is preferably 0.5 A / dm ² or more and 10 A / dm ² or less, for example. Even when a conductive substrate having a concave pattern is used as the pattern-like plating portion, the deposited copper is less likely to be a normal film when the first current density is increased.

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 value of the 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, the blackening process can be performed even when the second current density is 10 A / dm ² , and in some cases, the blacking process cannot be performed unless the current density is higher. 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 current densities may be changed stepwise to control the size of particles deposited as a blackened film.

  In the blackening process, finely divided copper metal is deposited on the surface of the copper layer formed in the conductive layer forming process by electroplating, thereby becoming black. This black color appears as a result of the deposition of finely divided copper metal on the conductive layer formed in the underlying conductive layer forming step, and such fine particles are arranged on the conductive layer. Therefore, it can be said that the black metal layer is formed by overlapping depending on the case.

  In order to quantitatively evaluate colors, numerical values are required, and several methods have been standardized by the International Commission on Illumination (CIE), but L * a * is a representative method. 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).

Substrates with a conductor layer pattern that shields the display surface of the display from electromagnetic waves are required to have good light transmittance. Therefore, it is preferable to reduce the coverage by the conductor layer pattern for shielding electromagnetic waves as much as possible, and to reflect external light. In order to enhance the brightness of transmitted light and improve the image quality, it is desirable that the conductor layer pattern itself be 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 black surface of the conductor layer pattern is raised, a black paper with a brightness of 25 is laid under the substrate with the conductor layer pattern, 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 black is insufficient and the original color of copper remains, the lightness L * shows a high value of 60 or more, and both the chromaticities a * and b * are larger than 5 indicating redness or yellow. .
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 2.8 or less, preferably 2 When the value is .6 or less, 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.
When the aperture ratio is less than 40% (including an aperture ratio of 0%, that is, including a solid copper foil), the chromaticity of the conductor layer pattern portion or the solid copper foil is measured against a black background having a brightness of 25 as described above. When the chromaticities a * and b * are both 5 or less, a good black color is exhibited, and particularly when the chromaticity a * and b * is 2.8 or less, a better black color is exhibited.

  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 the measuring instrument is a circle having a diameter of 10 mm, and the average color of the opening can be obtained.

  If the blackening treatment is continuously performed from the generation of the copper metal layer (copper foil) as in the present invention, 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. Therefore, the manufacturing time can be shortened and the cost can be reduced, and the environmental load can be reduced.

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

  Moreover, after plating using the conductive base material for plating, by peeling the copper foil or patterned copper foil (patterned copper metal) formed on the base material by a normal method, Copper foil or patterned copper foil can be obtained. In this case, as the substrate for peeling, a substrate in which an adhesive layer is laminated on another substrate is used, and the adhesive is applied to the copper foil surface of the conductive substrate for plating on which the patterned copper foil is formed. Alternatively, the substrate for peeling can be peeled and then peeled, and the patterned copper foil can be transferred to the substrate for peeling to peel the patterned copper foil from the conductive substrate for plating. The patterned copper foil is appropriately obtained by peeling from the peeling substrate.

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

The thickness of the metal deposited by plating on the tip of the convex portion of the conductive substrate having the insulating layer in the concave portion described above (plating thickness) exhibits sufficient conductivity (at this time, sufficient electromagnetic shielding properties are exhibited) In order to reduce the possibility of pinholes being formed in the conductor layer (in this case, the electromagnetic wave shielding property is reduced), the thickness is 3 μm or more. More preferably. 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 using the lightness 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 the present invention, a method for producing a base material with a conductor layer pattern using a conductive base material for plating having a patterned plating portion,
(A) a step of depositing a copper metal whose surface is blackened by plating on the plating part of the conductive base material for plating to generate a conductor layer pattern;
(B) including a step of transferring the copper metal deposited on the plating portion of the conductive substrate for plating to another substrate.
The process (a) is as described above. Hereinafter, the process (b) will be described.

  Examples of the substrate onto which the conductor layer pattern is transferred include a plate made of glass, plastic, etc., 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 the substrate to which the conductor layer pattern is transferred is preferably 0.5 mm to 5 mm from the viewpoint of protection of the display, strength, and handleability.

  The substrate to which the conductor layer pattern is transferred 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 plastic such as phon, polycarbonate, polyamide, polyimide, acrylic resin, etc., 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. Further, considering that the handleability is deteriorated if the film is too thin, 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 the substrate onto which the conductor layer pattern 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 preferably has adhesiveness at the time of transfer or exhibits adhesiveness under heating or pressurization. As the material having adhesiveness, 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. It is preferable to use a thermoplastic resin, a thermosetting resin, or a resin having a weight average molecular weight of 500 or more that is cured by irradiation with active energy rays. 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, 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. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, 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 for improving the adhesion. These copolymer resins can be used in combination of two or more as required.

  The resin used as the pressure-sensitive adhesive in the present invention may contain additives such as a crosslinking agent, a curing agent, a diluent, a plasticizer, an antioxidant, a filler, a colorant, an ultraviolet absorber, and a tackifier, as necessary. You may mix | blend.

  If the thickness of the pressure-sensitive adhesive layer is too thin, sufficient strength cannot be obtained. Therefore, when transferring the metal deposited by plating, the metal does not adhere to the pressure-sensitive adhesive layer, and transfer failure may occur. Therefore, the thickness of the adhesive layer is preferably 1 μm or more, and more preferably 3 μm or more in order to ensure transfer reliability during mass production. In addition, 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, increasing the chance of contacting the thin film insulating layer. It is preferably 30 μm or less, and more preferably 10 μm or less because it reduces the chance of contact between the thin film insulating layer and the adhesive layer.

  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 is deposited, the film is heated if necessary according to the characteristics of the pressure-sensitive adhesive.

  When applied to an electromagnetic wave shielding material, it is preferable that the line width of the conductor layer pattern of the substrate with the conductor layer pattern finally obtained is 40 μm or less and the line interval is 100 μm or more. Further, the line width is more preferably 25 μm or less from the viewpoint of invisibility of the conductor layer pattern (geometrical figure), 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 poor, so that the line width is preferably 1 μm or more. 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, and more preferably 60% or more. When the line interval becomes too large, the electromagnetic wave shielding property is lowered. 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 and 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.

  In addition, when applied to an electromagnetic shielding material, the thickness of the line of the conductor layer pattern is preferably 100 μm or less, and 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. Moreover, since it also shortens the time taken to deposit the metal by electroplating, it is more preferably 40 μm or less, and even more preferably 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.

  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 because it satisfies requirements such as high contrast and a black screen when the display is turned off. In the present invention, the step of blackening is performed by depositing a metal on the upper surface of the convex portion of the conductive substrate and then using the same plating bath as that for forming the conductor layer before transferring it to another substrate. Can do. It can also be performed after transferring to another substrate.

  When the blackening treatment step is performed after transfer 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. The step of forming these blackening treatment layers can be performed before or after the metal is deposited on the upper surface of the convex portion of the conductive base material, and before transferring to another base material, or transferred to another base material. It can be done later.

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.

  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.

  An example of a method for producing a substrate with a conductive layer pattern will be described with reference to FIG. 12, taking as an example the case where convex portions 3 (see FIG. 2B) having a trapezoidal cross section are formed on a conductive substrate. To do.

  First, in FIG. 12A, the insulating layer 6 is formed on the entire surface of the conductive substrate 1 having the convex portion 3 pattern having the upper surface 4 and the concave portion of the geometric drawing drawn thereby. It is sectional drawing which shows the state which carried out. As described above, the insulating layer 6 can be formed by wet coating (including electrodeposition coating), dry coating such as DLC, GLC, sputtering or vapor deposition. Of the insulating layer 6, the upper surface of the convex portion 3 is polished until the upper surface 4 of the convex portion 3 is exposed. FIG. 12B shows a cross-sectional view of this state.

  Next, the conductive base material 1 having the insulating layer in the concave portion and having the upper surface 4 of the convex portion 3 exposed is plated to deposit the metal 11 on the upper surface 4 of the convex portion 3. FIG. 12C shows a cross-sectional view of this state. Next, the surface of the metal 11 is blackened, and the metal 11 is changed to a blackened metal 11 ′. FIG. 12D shows a cross-sectional view of this state.

  Next, a film in which the adhesive layer 13 is applied to another substrate 12 is bonded to the surface of the conductive substrate 1 on which the blackened metal 11 ′ is present. FIG. 12E shows a cross-sectional view of this state. When the film having the pressure-sensitive adhesive layer 13 formed by applying a pressure-sensitive adhesive to the transparent substrate 12 is bonded to the surface on which the blackened metal 11 ′ is present, depending on the characteristics of the pressure-sensitive adhesive, Heated if necessary.

  And by peeling the film which apply | coated the adhesion layer 13 to the said another base material 12, the metal 11 'by which the blackening process was carried out adheres to the adhesion layer 13, and peels from the electroconductive base material 1, namely, It transfers to another base material and the base material 14 with a conductor layer pattern will be obtained. A cross-sectional view of this state is shown in FIG.

  The conductor layer pattern of the base material with a conductor layer pattern obtained above is blackened to obtain a base material with a conductor layer pattern having a blackened conductor layer pattern. FIG. 13 shows a cross-sectional view of this. In FIG. 13, a conductor layer pattern 11 whose surface has been blackened to become a black layer 15 (that is, a conductor layer pattern whose surface has been blackened) is attached to another substrate 12 via an adhesive layer 13. Are combined.

  Further, in FIG. 14, the conductor layer pattern 11 having the black layer 16 is bonded to another substrate 12 through the adhesive layer 13, which is the black color of the substrate with the conductor layer pattern shown in FIG. 13. The non-blackened surface of the blackened conductor layer pattern is blackened.

  When using a substrate with a conductor layer pattern having the above-described blackened conductor layer pattern as an electromagnetic wave shielding member on the front surface of the display, make sure that the surface on which the black layer is provided faces the viewer side of the display. Used.

  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. 15 shows a cross-sectional view of an electromagnetic wave shielding body obtained by sticking a base material with a conductor layer pattern to another base material. In FIG. 15, a blackened conductor layer pattern 11 ′ is embedded in the adhesive 13 laminated on the substrate 12, and the adhesive layer and the conductor layer pattern are covered with another substrate 17. This is because there is a blackened conductor layer pattern 11 ′ of a base material with a conductor layer pattern obtained by transferring the blackened conductor layer pattern 11 ′ to the base material 12 via the adhesive 13. The surface can be produced by a method in which the surface is pressure-bonded to another substrate 17 with an appropriate pressure. In this case, the conductive layer pattern 11 ′ that has been blackened by embedding an appropriate pressure while the adhesive layer 13 has sufficient fluidity or has sufficient fluidity is embedded in the adhesive 13. .
In this electromagnetic wave shielding body, the adhesive layer 13 and the other base material 17 are in direct contact with each other, and good adhesion can be obtained. Moreover, the base material 17 and the base material 12 can obtain an electromagnetic wave shielding body with high transparency by using a material having transparency and excellent surface smoothness.

  In FIG. 16, the transparent resin 18 covers the top of the substrate with the conductor layer pattern in which the conductor layer pattern 11 ′ that has been blackened through the adhesive layer 13 is bonded to the substrate 12.

  FIG. 17 shows a cross-sectional view of an electromagnetic wave shielding body according to another aspect. In this electromagnetic wave shielding body, the electromagnetic wave shielding member shown in FIG. 16 is a surface opposite to the surface on which the conductor layer pattern of the base material 12 is provided, and another base material 20 is bonded via an adhesive 19.

  FIG. 18 further shows a cross-sectional view of another embodiment of the electromagnetic wave shielding body. In FIG. 18, a conductive layer pattern made of a metal 11 'blackened through a pressure-sensitive adhesive layer 13 is bonded to a base material (another base material) 12, on which an adhesive or pressure-sensitive adhesive made of a transparent resin It is covered with an agent 21 and a protective film 22 is further laminated thereon. Another base material 20 such as a glass plate is attached to the other surface of the base material 12 via an adhesive layer 19. In this electromagnetic wave shielding member, the surface on which the conductor layer pattern of the substrate with the conductor layer pattern having the conductor layer pattern adhered to the substrate (another substrate) 12 via the pressure-sensitive adhesive 13 exists is transparent resin 21. Then, a protective film 22 is further laminated, and then an adhesive is applied to the other surface (the surface where nothing is laminated) of the base material 12 of the obtained laminate to form an adhesive layer 19. It can be manufactured by pressing this against another substrate 20 and bonding. As the transparent resin 21, in addition to the thermoplastic resin and the thermosetting resin, a resin curable with active energy rays can 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.

  By using the rotating body, the structure can be obtained as a scroll while continuously peeling the pattern formed by electroplating. That is, in FIG. 19, 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. A black film can be deposited on the deposited conductor layer pattern by applying a voltage higher than that between the anode 103 and the rotating body 104 during this period. 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. 19, the anode 103 for performing a conductive layer forming step for forming a 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 a blackening treatment step for depositing a metal so that the surface thereof becomes black is immersed in the plating solution apart from each other. In between, the interruption | blocking member 151 comprised with the insulator may be provided. 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 is communicated 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. 21, 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.

  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 It also serves as a second anode for performing a blackening treatment step for depositing metal so that its surface is black, and after the formation of the conductive layer under the first current density, the second anode The blackening treatment step may be performed under a current density of.

  The conductive substrate for plating having the convex pattern described in detail above and the concave portion of the geometric drawing drawn by the convex pattern and having the insulating layer in the concave portion has the convex pattern and the geometric drawn thereby. The concave portion having the illustrated insulating layer is formed 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 convex portions can be the one described above.
(1) Mesh-like geometric pattern (2) Rectangular 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 protrusions in the region B, the formation of the insulating layer, and the like can be performed in the same manner as the region A described above. Further, the height of the exposed portion of the convex portion, the width does not increase as the exposed portion proceeds in the tip direction, and the width is made smaller at the upper portion than at the lower portion as a whole, and the relationship d ₁₀ / h ₁₀ Etc. are preferably the same as those in the region A.

  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. 20A, 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. The base material with a conductor layer pattern in the present invention can be used as a transparent conductive film, and can also be used for applications similar to ITO conductive films.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
A resist film (Photech H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 750 × 1100 mm stainless steel plate (SUS304, finish 3 / 4H, thickness 100 μm, manufactured by Nisshin Steel Co., Ltd.). 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, a negative film formed in a lattice shape with a line width of the light transmission portion of 30 μm, a line pitch of 300 μm, and a bias angle of 45 ° was left on a stainless steel plate to which a resist film was bonded. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above the negative film under a vacuum of 600 mmHg or less. further. By developing with a 1% aqueous sodium carbonate solution, a resist mask having a line width of 30 μm, a line pitch of 300 μm, and a bias angle of 45 ° was formed on the SUS plate. Furthermore, the SUS plate was etched using a ferric chloride aqueous solution (45 ° B, manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching was performed until the line width of the SUS plate became 20 μm. Next, using a 5% sodium hydroxide solution, the resist film formed on the SUS plate is peeled off to form a lattice pattern (line width, ie, the width of the upper surface of the convex portion is 20 μm, the pitch is 300 μm, the convex portion 15 μm in height, the cross-sectional shape of the convex part is a curved surface (similar to FIG. 2 c), the pattern of the convex part having the upper surface, and the conductive base for plating having the concave part of the geometrical figure shape drawn thereby A material was prepared.

  In addition, the ground corresponding | compatible part (area | region B) of the mesh-like pattern of a convex part was formed in the outer peripheral part 40mm of the electroconductive base material for plating with the width | variety 80 micrometers of a convex part upper surface, the pitch of 300 micrometers, and the height of a convex part.

(Preparation of a conductive substrate having an insulating film)
Next, the conductive base material is used as a cathode, and the anode is used as a titanium plate. In a cationic electrodeposition paint (Insulated 3020, manufactured by Nippon Paint Co., Ltd.), it is etched in a lattice pattern under the condition of 15 V for 10 seconds. A stainless steel plate was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, baking was performed at 190 ° C. for 25 minutes. The coating thickness of the electrodeposition paint was 2.5 μm.

  Further, the electrodeposited stainless steel plate was polished with an abrasive powder (alumina solution B 0.05 μm, manufactured by Refinetech Co., Ltd.) and a polishing cloth (CONSUMABLES, manufactured by BUEHLER), and the upper surface portion of the convex portion was polished. Was exposed to produce a conductive substrate having an insulating film. The thickness of the electrodeposition coating film on the upper end portion of the convex portion of the conductive substrate was 2.5 μm, and the thickness of the electrodeposition coating film on the concave portion was 2.5 μm. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.

(Copper plating)
Subsequently, the electroconductive base material which has an insulating film was fixed to the rotating drum electrode used as a cathode using a Teflon (trademark) tape, and electrolytic copper plating was performed. The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.

Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Ammonia water (30%) consumption: 2 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: Copper plate The plating bath was stirred only by gentle liquid circulation. The top surface of the convex portion of the conductive substrate was plated at a current density of 20 A / dm ² until the deposited metal thickness was 5 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. Thereafter, 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)
A primer (HP-1, manufactured by Hitachi Chemical Co., Ltd.) on the surface of a polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm and a thickness of 1 μm as an adhesive layer. Polymers (HTR-280, manufactured by Nagase ChemteX Corporation) were sequentially applied to a thickness of 10 μm to prepare an adhesive film.

(Transcription)
The pressure-sensitive adhesive surface of this pressure-sensitive adhesive film and the surface having the copper plating in which the surface of the conductive base material was blackened were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C. and a pressure of 0.1 MPa. Subsequently, when the adhesive film bonded to the conductive substrate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive film.
Thereby, the base material with a conductor layer pattern which consists of a metal pattern with a line width of 28 μm, a line pitch of 300 μm, and a conductor thickness of 5 μm was obtained. As a result of observing the conductive substrate after the transfer, there was no portion where the insulating film was peeled off.

(Formation of protective film)
The surface of the base material with the conductor layer pattern obtained by the above blackening treatment is coated with UV curable resin Hitaroid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) and a polycarbonate film ( Macro hole DE, manufactured by Bayer Co., Ltd., 75 μm), the conductor layer pattern was buried in the UV curable resin, and then irradiated with 1 J / cm ² of ultraviolet rays using an ultraviolet lamp to give the UV curable resin. It was cured to obtain a substrate with a conductor layer pattern having a protective film.

(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 the reflection mode by placing black paper with a lightness L * = 25 on the bottom of the substrate.

  The object to be measured is an earth part formed outside the conductor layer pattern whose surface is blackened, and the opening area of the earth part is about 50%. As a result of the measurement, the lightness L * was 34, which was within a preferable range. The chromaticity was 0.4 for a * and 0.9 for b *, both of which were low in hue.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
A lattice-like pattern (upper surface width 7 μm, pitch 300 μm, convex) is formed on the SUS plate in the same manner as in Example 1 except that etching is performed until the width of the upper surface of the convex portion formed on the SUS plate is 7 μm. A conductive substrate having a height of 30 μm and a convex section having a curved surface (similar to FIG. 2 (c)) and having a convex pattern and a concave portion of the geometrical shape drawn thereby. Got.

(Preparation of a conductive substrate having an insulating film)
Next, the conductive group is used in an anionic electrodeposition coating (AMG-5E / 5W, manufactured by Shimizu Co., Ltd.) with the conductive substrate as an anode and a cathode as a titanium plate under the condition of 10 V 60 seconds. The material was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, baking was performed at 180 ° C. for 30 minutes. The coating thickness of the electrodeposition paint was 2.6 μm. Further, the electrodeposited conductive base material is polished with an abrasive powder (Type 0.1R, manufactured by Baikalox) and a polishing cloth (CONSUMABLES, manufactured by BUEHLER) to expose the upper surface portion of the convex portion, and the SUS surface is exposed. A conductive substrate having an insulating film was produced. The thickness of the electrodeposition coating film on the upper end portion of the convex portion of this conductive substrate was 0.2 μm, and the thickness of the electrodeposition coating film on the concave portion was 2.6 μm. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.

(Copper plating)
Subsequently, the electroconductive base material which has an insulating film was fixed to the rotating drum electrode used as a cathode using a Teflon (trademark) tape, and electrolytic copper plating was performed. The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.

Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Amount of ammonia water (30%) used: 2 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: The copper plate plating bath was stirred only by gentle liquid circulation. The top surface of the convex portion of the conductive substrate was plated at a current density of 20 A / dm ² until the deposited metal thickness was 3 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. Thereafter, 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, washed with water, and dried.

(Preparation of adhesive film)
Subsequently, the following resin composition 1 was apply | coated to 125-micrometer-thick PET film (A-4100, the Toyobo Co., Ltd. make) so that dry application | coating thickness might be 5 micrometers, and the adhesive film was produced.

Composition of Resin Composition 1 Byron UR-1350 (manufactured by Toyobo Co., Ltd., polyester resin)
100 parts by weight Coronate L (made by Nippon Polyurethane Co., Ltd., isocyanate compound)
3 parts by weight.

(Transcription)
Subsequently, the adhesive agent surface of the adhesive film obtained above and the surface having copper plating in which the surface of the conductive base material was blackened were bonded together using a roll laminator. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.1 MPa, and a line speed of 0.3 m / min. Since lamination was performed at a temperature exceeding the glass transition point (Tg) of the adhesive, tackiness was developed on the adhesive surface. Next, when the adhesive film was peeled from the conductive substrate, copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive surface. In this way, a metal pattern having a line width of 11 μm, a line pitch of 300 μm, and a conductor thickness of 3 μm and a blackened surface was transferred onto the adhesive film to obtain a substrate with a conductor layer pattern of the present invention.

(Formation of protective film)
After coating the surface of the substrate with the conductor layer pattern obtained above on which the conductor layer pattern exists in the same manner as in Example 1, UV curable resin Hitaroid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) was coated, and then a PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 μm) was laminated with a UV curable resin, and the conductor layer pattern was embedded in the UV curable resin. Furthermore, after UV rays of 1 J / cm ² were irradiated using an ultraviolet lamp to cure the UV curable resin, the PET film (A-4100, manufactured by Toyobo Co., Ltd., 75 μm) was peeled off to form a protective film. The base material with a conductor layer pattern was obtained.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained base material with a conductor layer pattern were measured by the method described in Example 1 including the measurement target. The lightness L * was 38, which was within a preferable range. The chromaticity was 0.5 for a * and 0.8 for b *, both of which were low in hue.

(Preparation of a conductive substrate having a convex pattern having an upper surface and a geometrical figure-shaped concave portion drawn thereby)
Using stainless steel (SUS316L finish 2B Nisshin Steel Co., Ltd., thickness 300 μm), except that etching was performed until the line width of the convex portion became 15 μm, the same conditions as in Example 1 were performed. A pattern (line width 15 μm, pitch 300 μm, convex height 20 μm), convex sectional shape is a curved surface (similar to FIG. 2 c), and a convex pattern having an upper surface and drawn thereby A conductive substrate having a geometrical figure-shaped recess was obtained.

(Preparation of a conductive substrate having an insulating film)
Next, in the same manner as in Example 2, the conductive substrate was used as an anode, the cathode was used as a titanium plate, and an anion-type electrodeposition paint (AMG-5E / 5W, manufactured by Shimizu Co., Ltd.) under conditions of 10 V 60 seconds. Then, the conductive base material was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, baking was performed at 180 ° C. for 30 minutes. The coating thickness of the electrodeposition paint was 2.8 μm. Further, the electrodeposited conductive base material is polished with an abrasive powder (Type 0.1R, manufactured by Baikalox) and a polishing cloth (CONSUMABLES, manufactured by BUEHLER) to expose the upper surface portion of the convex portion, and the SUS surface is exposed. A conductive substrate having an insulating film was produced. The thickness of the electrodeposition coating film on the upper end portion of the convex portion of the conductive substrate was 0.2 μm, and the thickness of the electrodeposition coating film on the concave portion was 2.8 μm. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion.

(Copper plating)
Subsequently, the electroconductive base material which has an insulating film was fixed to the rotating drum electrode used as a cathode using a Teflon (trademark) tape, and electrolytic copper plating was performed. The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.

Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Amount of ammonia water (30%) used: 2 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: Copper plate The plating bath was stirred only by gentle liquid circulation. The top surface of the convex portion of the conductive substrate was plated at a current density of 20 A / dm ² until the thickness of the deposited metal reached 7 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. Thereafter, 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 subsequently washed with water and dried.

(Preparation of adhesive film)
Subsequently, the following resin composition 2 was apply | coated to the easily bonding surface of 100-micrometer-thick PET film (A-4100, Toyobo Co., Ltd. product) so that dry application | coating thickness might be 15 micrometers, and the adhesive film was produced.

Composition of resin composition 2 AS-406 (manufactured by Yushi Kogyo Co., Ltd., acrylic polymer)
100 parts by weight Tetrad X (manufactured by Mitsubishi Gas Chemical Co., Inc., curing agent) 2 parts by weight.

(Transcription)
The pressure-sensitive adhesive surface of the pressure-sensitive adhesive film obtained above and the surface having copper plating on which the surface of the conductive base material was blackened were bonded 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. Next, when the adhesive film was peeled from the conductive substrate, the copper (blackened) deposited on the tip (exposed portion) of the convex portion of the conductive substrate was transferred to the adhesive surface of the adhesive film. It was. In this way, the metal pattern further blackened with a line width of 17 μm, a line pitch of 300 μm, and a conductor thickness of 7 μm was selectively transferred onto the adhesive film to produce a substrate with a conductor layer of the present invention.

(Manufacture of electromagnetic shielding material)
The adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was applied to a glass sheet having a thickness of 2 mm and laminated. Lamination conditions were a temperature of 25 ° C., a pressure of 0.5 MPa, and a line speed of 0.5 m / min. By the roll laminating, the conductor layer pattern having a thickness of 1 μm was embedded in the pressure-sensitive adhesive, and a highly transparent electromagnetic wave shielding body was obtained.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained base material with a conductor layer pattern were measured by the method described in Example 1 including the measurement target. The lightness L * was 38, which was within a preferable range. The chromaticity was 0.5 for a * and 0.8 for b *, both of which were low in hue.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
As stainless steel, SUS316L (finish 2B made by Nisshin Steel Co., Ltd., thickness 300 μm, size 250 mm × 350 mm (the same size as the outer periphery of the drum so that it can be wound around the drum)) A grid-like pattern is arranged with a line width of 30 μm, a line pitch of 300 μm, a bias angle of 45 °, and a line width of a light transmitting portion of 100 μm, a line pitch of 300 μm, and a bias angle of 45 on the outer periphery (width 20 mm). A negative film having a lattice pattern at 0 ° is used, and the rest is performed under the same conditions as in Example 1, and a conductive pattern having a convex pattern having an upper surface and a geometrical figure-shaped concave portion drawn thereby. A material was prepared. The central portion of the conductive base material is a lattice pattern having a width of 15 μm on the upper surface of the convex portion, a pitch of the convex portion of 300 μm, and a height of the convex portion of 20 μm (the sectional shape of the convex portion is the same as in FIG. 2C). The outer peripheral part (width 20 mm) is a convex-like mesh pattern with a width of 80 μm on the upper surface of the convex part, a pitch of 300 μm, and a height of the convex part of 15 μm (the cross-sectional shape of the convex part is the same as in FIG. Met. This outer peripheral part corresponds to the earth part of the electromagnetic wave shielding member.

(Preparation of conductive substrate for plating with insulating film)
Next, in the same manner as in Example 2, the above conductive base material was used as an anode, the cathode was used as a titanium plate, and an anionic electrodeposition paint (AMG-5E / 5W, manufactured by Shimizu Corporation) under conditions of 10 V 60 seconds. Then, the conductive substrate was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, baking was performed at 180 ° C. for 30 minutes. The coating thickness of the electrodeposition paint was 2.8 μm. Further, the electrodeposited conductive base material is polished on the upper surface portion of the convex portion using polishing powder (Type 0.1R, manufactured by Baikowski Chimie SA) and a polishing cloth (CONSUMABLES, manufactured by Bühler GMBH), and the SUS surface is polished. An electroconductive substrate for plating having an insulating film was exposed. The thickness of the electrodeposition coating film on the upper end portion of the convex portion of the conductive substrate for plating was 0.2 μm, and the thickness of the electrodeposition coating film on the concave portion was 2.8 μm. This electroconductive substrate for plating was covered with an insulating film except for the upper surface of the convex portion.

(Copper plating)
Next, the conductive substrate for plating having an insulating film was fixed to a rotating drum electrode serving as a cathode using a Teflon (registered trademark) tape, and electrolytic copper plating was performed.

  The main specifications of the rotating drum electrode are as follows.

Drum diameter: 110 mm
Drum width: 250mm
Plating tank: diameter 250mm, height: 300mm, liquid capacity: 8L
Anode: Copper plate Drum rotation speed: 10rpm
The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.

<Bath composition>
Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Amount of ammonia water (30%) used: 2 mL / L
<Electrolysis conditions>
pH: 8-9
Bath temperature: 30 ° C
The upper surface of the convex portion of the conductive substrate for plating wound around the drum was plated at a current density of 10 A / dm ² until the thickness of the deposited metal became 3 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. Thereafter, the current density was changed to 30 A / dm ² and plating was continued for 5 seconds to blacken the surface. The conductive substrate for plating with the conductive layer pattern whose surface was blackened was subsequently washed with water and dried.

(Preparation of adhesive film)
Subsequently, the following resin composition 2 was apply | coated to the easily bonding surface of 100-micrometer-thick PET film (A-4100, Toyobo Co., Ltd. product) so that dry application | coating thickness might be 15 micrometers, and the adhesive film was produced.

<Composition of Resin Composition 2>
AS-406 (manufactured by Yushi Co., Ltd., acrylic polymer)
100 parts by weight Tetrad X (manufactured by Mitsubishi Gas Chemical Co., Inc., curing agent) 2 parts by weight.

(Transcription)
Blackening treatment of the adhesive film obtained above using a roll laminator so that the adhesive surface and the blackened copper plating on the conductive substrate for plating wound around the drum are in contact with each other Bonded to the copper plating.

  Lamination conditions were a roll laminator roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 0.5 m / min. Next, when the adhesive film was peeled off from the conductive substrate for plating, copper (having a black metal layer) deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive surface of the adhesive film. . In this way, the conductor layer pattern further blackened with a line width of 20 μm, a line pitch of 300 μm, and a conductor thickness of 3 μm was selectively transferred onto the adhesive film to produce a substrate with a conductor layer pattern of the present invention.

(Manufacture of electromagnetic shielding material)
The adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was applied to a glass having a thickness of 2 mm and laminated. Lamination conditions were a temperature of 25 ° C., a pressure of 0.5 MPa, and a line speed of 0.5 m / min. By the roll lamination, the conductor layer pattern having a thickness of 3 μm was embedded in the pressure-sensitive adhesive, and a highly transparent electromagnetic wave shielding body was obtained.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained base material with a conductor layer pattern were measured by the method described in Example 1 including the measurement target. The lightness L * was 38, which was within a preferable range. The chromaticity was 0.5 for a * and 0.8 for b *, both of which were low in hue.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
As stainless steel, SUS316L (finish 2B made by Nisshin Steel Co., Ltd., thickness 300 μm, size is 750 mm × 1100 mm) and negative film, the light transmitting part has a line width of 30 μm, the line pitch is 300 μm, and the bias angle is 300 μm. Uses a negative film in which a lattice pattern is arranged at 45 °, and the outer periphery (width 20 mm) has a light transmission portion line width of 100 μm, a line pitch of 300 μm, a bias angle of 45 °, and a lattice pattern. The rest was carried out under the same conditions as in Example 1, and a conductive substrate having a convex pattern having an upper surface and a geometrical figure-shaped concave portion drawn thereby was produced. The central portion of the conductive base material is a lattice pattern having a width of 15 μm on the upper surface of the convex portion, a pitch of the convex portion of 300 μm, and a height of the convex portion of 20 μm (the sectional shape of the convex portion is the same as in FIG. 2C). The outer peripheral part (width 20 mm) is a convex-like mesh pattern with a width of 80 μm on the upper surface of the convex part, a pitch of 300 μm, and a height of the convex part of 15 μm (the cross-sectional shape of the convex part is the same as in FIG. 2-c). Met. This outer peripheral part corresponds to the earth part of the electromagnetic wave shielding member.

(Preparation of conductive substrate for plating with insulating film)
Next, in the same manner as in Example 2, the above conductive base material was used as an anode, the cathode was used as a titanium plate, and an anionic electrodeposition paint (AMG-5E / 5W, manufactured by Shimizu Corporation) under conditions of 10 V 60 seconds. Then, the conductive substrate was electrodeposited. After washing with water and drying at 100 ° C. for 10 minutes, baking was performed at 180 ° C. for 30 minutes. The coating thickness of the electrodeposition paint was 2.8 μm. Further, the electrodeposited conductive base material is polished on the upper surface portion of the convex portion using polishing powder (Type 0.1R, manufactured by Baikowski Chimie SA) and a polishing cloth (CONSUMABLES, manufactured by Bühler GMBH), and the SUS surface is polished. An electroconductive substrate for plating having an insulating film was exposed. The thickness of the electrodeposition coating film on the upper end portion of the convex portion of the conductive substrate for plating was 0.2 μm, and the thickness of the electrodeposition coating film on the concave portion was 2.8 μm. This electroconductive substrate for plating was covered with an insulating film except for the upper surface of the convex portion.

(Copper plating)
Next, the conductive substrate for plating having an insulating film was fixed to a rotating drum electrode serving as a cathode using a Teflon (registered trademark) tape, and electrolytic copper plating was performed.

  The main specifications of the rotating drum electrode are as follows.

Drum diameter: 425mm
Drum width: 900mm
Plating tank: diameter 600mm, liquid capacity: 80L
Anode: Insoluble electrode plate Drum rotation speed: 0.4 rpm
The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.

<Bath composition>
Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Amount of ammonia water (30%) used: 2 mL / L
<Electrolysis conditions>
pH: 8-9
Bath temperature: 30 ° C
The upper surface of the convex portion of the conductive substrate for plating wound around the drum was plated at a current density of 10 A / dm ² until the thickness of the deposited metal became 5 μm. The metal deposited at this stage was red and the conductivity was 0.08Ω / □. Thereafter, the current density was changed to 30 A / dm ² and plating was continued for 5 seconds to blacken the surface. The conductive substrate for plating with the conductive layer pattern whose surface was blackened was subsequently washed with water and dried.

(Preparation of adhesive film)
Subsequently, the following resin composition 2 was apply | coated to the easily bonding surface of 125-micrometer-thick PET film (A-4100, Toyobo Co., Ltd. product) so that dry application | coating thickness might be set to 15 micrometers, and the adhesive film was produced.

<Composition of Resin Composition 2>
AS-406 (manufactured by Yushi Co., Ltd., acrylic polymer)
100 parts by weight Tetrad X (manufactured by Mitsubishi Gas Chemical Co., Inc., curing agent) 2 parts by weight.

(Transcription)
Blackening treatment of the adhesive film obtained above using a roll laminator so that the adhesive surface and the blackened copper plating on the conductive substrate for plating wound around the drum are in contact with each other Bonded to the copper plating.

  Lamination conditions were a roll laminator roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 0.5 m / min. Next, when the adhesive film was peeled off from the conductive substrate for plating, copper (having a black metal layer) deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive surface of the adhesive film. . In this way, the conductor layer pattern further blackened with a line width of 25 μm, a line pitch of 300 μm, and a conductor thickness of 5 μm was selectively transferred onto the adhesive film to produce a substrate with a conductor layer pattern of the present invention.

(Manufacture of electromagnetic shielding material)
The adhesive surface (surface having a conductor layer pattern) of the substrate with a conductor layer pattern obtained above was applied to a glass having a thickness of 2 mm and laminated. Lamination conditions were a temperature of 25 ° C., a pressure of 0.5 MPa, and a line speed of 0.5 m / min. By the roll lamination, the conductor layer pattern having a thickness of 5 μm was embedded in the pressure-sensitive adhesive, and a highly transparent electromagnetic wave shielding body was obtained.

(Measurement of brightness and chromaticity)
About the brightness and chromaticity of the obtained base material with a conductor layer pattern, the measurement object is a conductor layer pattern in which the surface having an opening area of about 80% is blackened, and otherwise the same as in Example 1. It was measured. The lightness L * was 40.9, which was within a preferable range. Further, the chromaticity was 2.2 for a * and 1.75 for b *, and both values were low in hue.

(Comparative Example 1)
In (copper plating) of Example 1, the substrate with a conductor layer pattern was subjected to electrolytic copper plating in a copper sulfate plating solution having the following composition and conditions.

(Composition of electrolytic copper plating solution)
Concentration of copper sulfate pentahydrate: 220 g / L,
Concentration of sulfuric acid: 50 g / L
Concentration of hydrochloric acid: 50ppm
pH: 1-3
Bath temperature: 30 ° C
Anode: Copper plate As in Example 1, stirring of the plating bath was only gentle circulation. The top surface of the convex portion of the conductive substrate was plated at a current density of 20 A / dm ² until the deposited metal thickness was 5 μm. Thereafter, the current density was changed to 50 A / dm ² and plating was continued for 5 seconds. However, the deposited conductor layer could not be blackened.

(Manufacture of copper foil without pattern)
Electrolytic copper plating was performed on a 750 × 1100 mm stainless steel plate (SUS304, finish 3 / 4H, thickness 100 μm, manufactured by Nisshin Steel Co., Ltd.) in a copper plating solution having the following composition and conditions as in Example 1. It was.

(Composition of electrolytic copper plating solution)
Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 200 g / L
Amount of ammonia water (30%) used: 5 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: Copper plate

Copper plating was performed at a current density of 2 A / dm ² until the thickness of the deposited metal reached 5 μm in the recesses of the conductive substrate. The deposited metal at this stage was a red continuous film. Next, the current density was changed to 4 A / dm ² , followed by plating for 5 seconds. As a result, a metal copper foil having a thickness of 5 μm and a black surface was obtained. When the brightness and chromaticity of the obtained copper foil were measured with the spectrocolorimeter described in Example 1 set to the reflection mode, the brightness L * was 33, the chromaticity a * was 0.5, and the b * was −. 0.1.

(Preparation of conductive substrate for plating)
A negative photoresist (SU-8, manufactured by Nippon Kayaku Co., Ltd.) was applied to one surface of a 150 mm square SUS304 (surface # 600 polished) plate with a spin coater to a film thickness of 5 μm at 65 ° C. The substrate was heated for 3 minutes at 95 ° C. for 7 minutes on a hot plate and dried to obtain a substrate (conductive substrate) having a photoresist film.
Next, a lattice mask having a line width of 30 μm and a pitch of 300 μm was brought into close contact with the surface of the photoresist film of the substrate, exposed at 300 mJ / cm ² , and further heated in an oven at 95 ° C. for 15 minutes. The substrate having the exposed photoresist film was rocked in propylene glycol monomethyl ether acetate for 90 seconds to develop the photoresist film, and then washed with 2-propanol. In this way, a conductive substrate with a resist pattern having a lattice-shaped recess in which the conductive substrate was exposed as a bottom surface was obtained. Next, the conductive substrate with a resist pattern was baked by heating at 150 ° C. for 30 minutes and then at 200 ° C. for 15 minutes to obtain a conductive substrate for plating.
The obtained conductive substrate for plating had a line width (width of recesses) of 23.5 μm and a pitch (pitch of recesses) of 300 μm.
(Copper plating)
Using the conductive substrate for plating, electrolytic copper plating was performed in a copper pyrophosphate plating solution having the following composition and conditions.
(Composition of electrolytic copper plating solution)
Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Amount of ammonia water (30%) used: 2 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: Copper plate The plating bath was stirred only by gentle circulation. The concave portions of the conductive substrate were plated at a current density of 5 A / dm ² until the deposited metal thickness was 8 μm. The deposited metal at this stage was a red continuous film, and the conductivity was 0.03Ω / □. Thereafter, the current density was changed to 50 A / dm ² and plating was continued for 5 seconds to blacken the surface. The conductive substrate for plating with the conductive layer pattern whose surface was blackened was subsequently washed with water and dried. The conductive layer pattern whose surface was blackened was peeled off from the electroconductive substrate for plating to obtain a grid-like copper mesh whose surface was blackened. Note that the resist mask formed on the conductive substrate was also peeled off at this time.
The lightness and chromaticity of the obtained conductor layer pattern were measured by the method described in Example 1 except that the object to be measured was a peeled conductor layer pattern. The lightness L * was 47.3, the chromaticity a * was 0.75, and the b * was 2.54, and a low value was obtained for each hue.

  The line width, pitch, and aperture ratio were measured based on micrographs. The thickness of the line and the thickness of the copper foil were measured by partially cutting the obtained conductive layer pattern with metal foil, casting it with a resin, and observing the cross section under a microscope. The visible light transmittance was measured using a double beam spectrophotometer (200-10 type, manufactured by Hitachi, Ltd.), and the transmittance was measured at 400 to 700 nm, and the average value was used. The presence or absence of pattern abnormality was confirmed with the naked eye using a magnifier. The electromagnetic wave shielding property was measured at a frequency of 300 MHz using the Advantest method. The durability of the conductive substrate was confirmed by directly observing the conductive substrate with a magnifier after plating and peeling. The color unevenness of the black treated surface of the substrate with the conductor layer pattern was visually confirmed.

The perspective view which shows an example of the electroconductive base material in which the geometric figure of the recessed part with respect to a convex part is formed. A part of AA sectional drawing of FIG. FIG. 3 is a part of a cross-sectional view taken along the line AA in FIG. Sectional drawing of the electroconductive base material of the state which formed the insulating layer on the surface in the electroconductive base material which has the pattern of a convex part and the geometrical drawing shape recessed part drawn by it. Sectional drawing which shows the other example of the electroconductive base material of the state which formed the insulating layer in the surface in the electroconductive base material which has the recessed part of the pattern of a convex part and the geometric drawing shape drawn by it. Sectional drawing which shows the other example of the electroconductive base material of the state which formed the insulating layer in the surface in the electroconductive base material which has the recessed part of the pattern of a convex part and the geometric drawing shape drawn by it. Sectional drawing which shows an example of the structure of the pattern of the convex part of the electroconductive base material in this invention, and the insulating layer of a convex part side surface. Sectional drawing which shows an example of the process which shows the preparation methods of the electroconductive base material for plating. Sectional drawing which shows an example of the process which shows the preparation methods of the electroconductive base material for plating. Sectional drawing which shows an example of the process which shows the preparation methods of the electroconductive base material for plating. Sectional drawing which shows an example of the process which shows the preparation methods of the electroconductive base material for plating. Sectional drawing which shows an example of the preparation methods of the base material with a conductor layer pattern using the produced plate for plating transcription | transfer. Sectional drawing of the base material with a conductor layer pattern which consists of a metal pattern by which the conductor layer pattern was blackened. Sectional drawing of the base material with a conductor layer pattern which consists of a metal pattern by which the conductor layer pattern was blackened. 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 top view of a conductor layer pattern. 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.

Explanation of symbols

1: conductive substrate for plating 2: concave portion 3: convex portion 4: upper surface of convex portion 5: side surface of convex portion 6: insulating layer 7: photocurable resin layer 8: insulating layer 9: adhesive film 10: mask layer 11: Metal, conductor layer pattern 11 ': Blackened conductor layer pattern 12, 14, 17, 20: Base material 13: Adhesive layer 15, 16: Black layer 18: Transparent resin 19: Adhesive layer 21: Adhesive 22: 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: Adhesion with conductive layer pattern Support 151: Blocking member

Claims (46)

  In the copper metal manufacturing method in which copper metal is deposited by plating on a conductive base material for plating and the surface of which is blackened, and the surface is blackened, the copper metal is deposited in layers under the first current density And a blackening treatment step of depositing copper metal on the surface of the copper metal layer under a second current density higher than the first current density so that the surface is black. Is performed in one copper pyrophosphate plating bath, a method for producing a copper metal layer having a blackened surface.   The copper metal 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. A method for producing a metal layer.   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 copper metal layer by which the surface of Claim 1 or 2 was blackened.   2. In the blackening treatment step, the metal is deposited so that the chromaticity a * and b * of the light transmission part having an aperture ratio of 40% or more are both 2.8 or less against a black background of brightness 25. Or the manufacturing method of the 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 copper metal layer by which the surface of Claim 1 or 2 made to deposit was blackened.   The surface according to any one of claims 1 to 5, wherein the copper pyrophosphate plating bath is an alloy plating bath containing one or more of group VI elements such as molybdenum and group VIII elements such as cobalt and nickel as additives. A method for producing a blackened copper metal layer. 1st current density is 0.5-40 A / dm < ² >, The manufacturing method of the copper metal layer by which the surface of any one of Claims 1-6 was blackened.   The method for producing a copper metal layer whose surface has been blackened according to any one of claims 1 to 7, wherein the conductive substrate for plating is a conductive substrate having a patterned plating portion.   The method for producing a copper metal layer having a blackened surface according to claim 8, wherein the conductive substrate for plating is a conductive substrate having a pattern of convex portions as a patterned plating portion.   The surface according to claim 9, wherein the conductive substrate for plating is a conductive substrate having a geometrical figure-shaped concave portion drawn by a pattern of convex portions, and copper metal is deposited on a tip portion of the convex portion. A method for producing a blackened copper metal layer.   The conductive base material for plating is covered with an insulating layer in the concave portion, but the tip portion of the convex portion is exposed, the width of the exposed portion is 1 μm to 40 μm, and an insulating layer is applied to the concave portion. The method for producing a copper metal layer whose surface has been blackened according to claim 10, wherein the height of the subsequent convex portion is 10 μm or more.   The method for producing a copper metal layer having a blackened surface according to claim 11, wherein the height of the convex portion after applying the insulating layer to the concave portion of the conductive substrate for plating is 10 μm or more.   The method for producing a copper metal layer having a blackened surface according to claim 11 or 12, wherein the thickness of the insulating layer of the conductive substrate for plating is 10 µm or less near the end of the side surface of the convex portion. The method for producing a copper metal layer having a blackened surface according to any one of claims 7 to 10, wherein the interval between the convex portions of the conductive substrate for plating is 100 µm to 1000 µm.
14. The surface according to claim 9, wherein an insulating layer is formed on a concave surface at a position lower than a position lower by 0.5 to 5 μm than an upper end of the convex portion of the conductive base material for plating. Method for manufacturing a copper metal layer subjected to chemical treatment.   9. The method for producing a copper metal layer having a blackened surface according to claim 8, wherein the conductive substrate for plating is a conductive substrate having a concave pattern as a patterned plating portion.   The method for producing a copper metal layer having a blackened surface according to any one of claims 1 to 15, wherein the electroconductive 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 while rotating the rotating body, a metal pattern manufacturing step and The manufacturing method of the copper metal by which the surface of any one of Claims 1-15 which performs a transfer process was blackened.   The surface according to any one of claims 1 to 17, wherein in the copper metal layer forming step, the copper metal is deposited so that the thickness of the copper metal is 0.1 to 20 µm in the plated portion of the conductive base material. A method for producing a blackened copper metal layer.   A first anode for performing a copper metal layer forming step of forming a copper metal layer under the first current density; and a surface of the conductive metal layer under the second current density. A second anode for performing a blackening treatment step for depositing metal so as to be black is immersed in the plating solution apart from each other, and an insulator is provided between the anodes. The method for producing a copper metal layer whose surface is blackened according to any one of claims 1 to 18, wherein a blocking member is provided.   A first anode for performing a copper metal layer forming step of forming a copper metal layer under the first current density; and a black surface on the surface of the copper metal layer under the second current density And the second anode for performing the blackening treatment step for depositing the metal so that the second current flows after the formation of the conductive layer under the first current density. The method for producing a copper metal layer whose surface is blackened according to claim 1, wherein the blackening treatment step is performed under a density.   After performing the manufacturing method of the copper metal layer by which the surface of any one of Claims 1-20 was blackened, the copper metal layer by which the surface was blackened is peeled from the electroconductive substrate for plating. A method for producing a copper metal whose surface is blackened. Metal pattern preparation step for depositing copper metal by electroplating on the plating portion of the conductive substrate for plating having a patterned plating portion, and a transfer step for transferring the copper metal deposited on the conductive substrate to the adhesive support In a method for producing a substrate with a conductor layer pattern comprising:
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 the blackening treatment step of depositing metal so that the surface is black is performed in one copper pyrophosphate plating bath.   23. With a conductor layer pattern according to claim 22, 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 process, the metal is deposited so that the light transmission part having an aperture ratio of 50% has a lightness of 25 to 50, or the chromaticities a * and b * are both 5 or less, with a black background of 25 The method for producing a substrate with a conductor layer pattern according to claim 22 or 23.   23. 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 against a black background of brightness 25. 24. A method for producing a substrate with a conductor layer pattern according to 23.   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 22 or 23 to deposit.   27. The conductor layer according to any one of claims 22 to 26, wherein the copper pyrophosphate plating bath is an alloy plating bath containing one or more of Group VI elements such as molybdenum and Group VIII elements such as cobalt and nickel as additives. A method for producing a patterned substrate. Method for producing a conductive layer patterned substrate according to any one of claims 22 to 27 the first current density is 0.5~40A / dm ^2.   The method for producing a base material with a conductor layer pattern according to any one of claims 22 to 28, wherein the conductive metal for plating has a pattern of convex portions as a patterned plating portion.   30. The conductor according to claim 29, wherein the conductive metal for plating is a conductive base material having a convex pattern and a concave portion having a geometrical shape drawn by the convex pattern, and deposits copper metal on a tip portion of the convex portion. The manufacturing method of a base material with a layer pattern.   Although the concave portion of the conductive substrate for plating is covered with an insulating layer, the tip portion of the convex portion is exposed, the width of the exposed portion is 1 μm to 40 μm, and the insulating layer is applied to the concave portion. The method for producing a base material with a conductor layer pattern according to any one of claims 29 and 30, wherein the height of the convex portion is 10 µm or more.   The manufacturing method of the base material with a conductor layer pattern of Claim 31 whose height of the convex part after giving an insulating layer to the recessed part of the electroconductive base material for plating is 10 micrometers or more.   The method for producing a base material with a conductor layer pattern according to claim 31 or 32, wherein the thickness of the insulating layer of the conductive base material for plating is 10 µm or less in the vicinity of the end of the convex side surface.   The manufacturing method of the base material with a conductor layer pattern of any one of Claims 29-33 whose space | interval of the convex part of the electroconductive base material for plating is 100 micrometers-1000 micrometers.   35. The conductor layer pattern according to any one of claims 29 to 34, wherein an insulating layer is formed on the concave surface at a position lower than a position 0.5 to 5 [mu] m lower than the upper end of the convex portion of the conductive substrate for plating. A manufacturing method of a substrate with a mark.   The method for producing a substrate with a conductor layer pattern according to any one of claims 22 to 28, wherein the conductive substrate for plating is a conductive substrate having a concave pattern as a patterned plating portion.   The method for producing a substrate with a conductor layer pattern according to claim 36, wherein the width of the recesses is 1 to 60 µm and the interval between the recesses is 50 to 1000 µm.   The method for producing a substrate with a conductor layer pattern according to any one of claims 22 to 37, 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 while rotating the rotating body, a metal pattern manufacturing step and The manufacturing method of the base material with a conductor layer pattern of any one of Claims 22-38 which performs a transcription | transfer process.   40. The conductor layer patterned base according to any one of claims 22 to 39, wherein in the conductive layer forming step, the metal is deposited so that the thickness of the metal is 0.1 to 20 [mu] m in the plated portion of the conductive base material. A method of manufacturing the material.   The method for producing a substrate with a conductor layer pattern according to any one of claims 22 to 40, wherein the metal used for plating contains at least one metal having a volume resistivity at 20 ° C of 20 µΩ / cm or less. In the manufacturing method of the base material with a conductor layer pattern of any one of Claims 22-41,
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. A second anode for performing a blackening treatment step for depositing metal so as to be black 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 22-41,
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. A second anode for performing a blackening treatment step for depositing a metal so as to be black 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 22-43.   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 44 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 44 with resin.

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