JP2009167523A - Conductive substrate for plating, method for manufacturing the same, conductive layer pattern using the same, and method for manufacturing substrate with conductive layer pattern, substrate with conductive layer pattern, and translucent electromagnetic wave shielding member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive substrate for plating with which more uniform plating is possible, and to manufacture a substrate with a conductor layer pattern by using a transfer process with high productivity. <P>SOLUTION: There are provided the substrate and a conductive diamond-like carbon (DLC) film formed on the surface of the substrate or a conductive substrate for plating including a conductive inorganic material film, and is more preferably a conductive substrate 2 formed with the conductive DLC film or the conductive inorganic material film. The substrate has an insulating layer 3 formed on the conductive DLC film or the conductive inorganic material film Recessed parts 4 for forming plating which are broader toward an opening direction are formed in the insulating layer 3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive substrate for plating, a method for producing the same, a method for producing a conductor layer pattern or a substrate with a conductor layer pattern using the same, a substrate with a conductor layer pattern, and a translucent electromagnetic wave shielding member.

  Various proposals have been made for methods for shielding electromagnetic waves on the display surface of a display that generates electromagnetic waves. For example, a method of applying an electromagnetic shielding coating over the shielded surface, a method of attaching a metal foil to the shielded surface, and an electromagnetic shielding sheet obtained by laminating a metal-plated fiber mesh to a resin sheet is attached to the shielded surface. Generally, a method, a method in which a conductive fiber knitted in a mesh shape is bonded to a shielded surface, and the like are performed.

  Among these, when shielding the electromagnetic wave on a transparent glass surface, a transparent resin panel surface, a display surface of a display such as a cathode ray tube (CRT) or a plasma display panel (PDP), etc., the electromagnetic wave shielding member is thin and transmits light. Electromagnetic wave shielding members using a metal mesh have become the mainstream as a material that has good properties (transparency) and balances electromagnetic wave shielding properties that are contrary to these in a balanced manner.

  As a method for producing an electromagnetic wave shielding member having a metal mesh as an electromagnetic wave shielding layer, Patent Document 1 discloses electrodeposition of metal using a metal electrolyte solution on an electrodeposition substrate capable of metal electrodeposition in a mesh shape, A method for producing an electromagnetic wave shielding plate by adhesion and transfer to an electromagnetic wave shielding substrate via an adhesive (hereinafter referred to as a transfer method) is described. The above electrodeposition substrate has an electrodeposited portion on which a metal pattern can be deposited in a mesh pattern by forming a reverse pattern to the mesh pattern with an insulating film that inhibits electrodeposition on a conductive substrate such as a metal plate. It is produced so as to be exposed. Patent Document 1 describes a method using an electrodeposition substrate in which a convex conductive mesh layer is formed on an insulating layer support.

  Patent Document 2 discloses a metal layer transfer base sheet for producing a circuit pattern of an electronic component or an electrode pattern of a ceramic capacitor. The base sheet for metal layer transfer includes a base metal layer and an electrical insulating layer, and a convex pattern for forming the transfer metal layer by electrolytic plating is formed on the surface of the base metal layer. The surface of the base metal layer is formed on the portion where the convex pattern is not formed. As a method of manufacturing a base sheet for transferring a metal layer, an etching resist is formed in the same pattern as a convex pattern on the surface of the base metal layer using a dry film resist or the like, and is exposed without being covered with the etching resist. The surface of the layer is etched to form a recess, after which the etching resist is removed, an electrical insulation layer is formed on the entire surface of the etched base metal layer, and then the electrical insulation layer until the convex pattern is exposed A method of polishing the surface is disclosed. At this time, the surface of the electrical insulating layer and the surface of the convex pattern of the base metal layer are arranged on the same plane and are flush with each other. As another example of the manufacturing method, an electrical insulating layer made of a plating resist is formed on the surface of the base metal layer in a reverse pattern (inverted pattern) using a dry film resist or the like to electrically insulate. An electroplated metal layer is formed in a convex pattern on the surface of the base metal layer exposed from between the layers. At this time, a method is described in which the thickness of the electroplated metal layer is made thicker than the electrical insulating layer. . By forming the surface of the electroplated metal layer higher than the surface of the electrical insulation layer, the electrical insulation layer is transferred to the adhesive sheet when the transfer metal layer formed by electroplating on the convex pattern is transferred to the adhesive sheet. It is described that the adhesive sheet can be prevented from being damaged.

  It is well known that the metal foil is not limited to the patterned metal foil as described above, and is manufactured by depositing a metal on a conductive substrate by electrolytic plating.

JP-A-11-26980 JP 2004-186416 A

  If there are scratches or small dents on the surface of the conductive substrate, uniform plating cannot be performed, and therefore a uniform metal foil cannot be formed. Inspection of such surface irregularities such as scratches and minute depressions also takes time and labor, and is problematic from the viewpoint of productivity.

The transfer method described in Patent Document 1 can be expected as a method capable of reducing the cost in producing the electromagnetic wave shielding member.
In Patent Document 1, it is described that an insulating layer is formed of a photoresist when producing an electrodeposition substrate. When such an electrodeposition substrate is used, it is repeated several times to several tens of times. Although it can be used, there is a problem that it cannot be used repeatedly several hundred to several thousand times and does not reach a mass production level. This is because the insulating layer forming the mesh pattern on the electrodeposition substrate is subjected to peeling stress due to adhesive transfer, and the insulating layer is peeled off from the conductive base material after a few repeated uses.
Further, an electrodeposited substrate is disclosed in which an insulating layer is formed by producing SiO ₂ on a conductive base material and photoetching this, but since photoetching is performed, the number of steps for producing the electrodeposited substrate is increased. There's a problem. There exists a problem that a recessed part becomes narrow toward an opening direction by overetching.
Further, in Patent Document 1, a concave portion necessary for photolithography or cutting is formed on the surface of a metal substrate, and then a strong insulating resin is embedded in the concave portion and cured to form a metal electrodeposition in a mesh shape. A method for producing an electrodeposition substrate having possible electrodeposition portions is disclosed. However, producing concave portions in the shape of a metal substrate by this method has problems in pattern accuracy, pattern defect-free, pattern production time, and the like, and cannot be said to be a method with good productivity. Further, when an insulating resin is used for the insulating layer, there is a problem in durability of the insulating layer.
In addition, in Patent Document 1, when a single metal plate such as tantalum or titanium, or the surface is such a metal surface, after forming a resist only in a portion corresponding to a portion constituting the electrodeposition portion, By forming an insulating oxide layer such as titanium oxide or tantalum oxide by anodic oxidation, and then removing the resist, an electrodeposition substrate having extremely high durability and extremely high reusability can be produced. It is disclosed that the anodic metal oxide layer has high hardness, is hard to be damaged, and has an insulating film that can sufficiently withstand electrodeposition pressure bonding.
However, in this case, including the above case, in the formed concave mesh pattern (electrodeposit), the insulating oxide layer formed by anodization is extremely thin and the cross section in the width direction is flush. In addition, since there is no shape unevenness, there is no action to shape the electrodeposition layer. That is, it can be said that it is difficult to control the shape of the electrodeposited line. In addition, an insulating oxide layer formed by anodization has poor durability and is not practically suitable for continuous work. In fact, in Ni electroforming, anodic oxidation before transfer is forced every time. Furthermore, an insulating oxide layer formed by anodization is not suitable for high-speed electroplating because of its low insulating property. However, in the case of an insulating oxide layer formed by anodizing aluminum, it can be said that the insulating property is relatively high, but the mechanical durability is poor.
Patent Document 1 describes a method of using an electrodeposition substrate in which a convex conductive mesh layer is formed on an insulating layer support. However, according to this method, the side surface of the conductive mesh is actually used. In addition, metal is electrodeposited, and this becomes resistance to the adhesion transfer of the mesh electrodeposited metal layer, and the mesh pattern cannot be peeled or even if it can be peeled off, the mesh pattern will be broken and the electromagnetic shielding properties will be reduced. The present inventors have confirmed that there is a problem that defects occur.

In Patent Document 2, an organic insulating resin is exemplified as a material for the electrical insulating layer. However, the surface of the electrically insulating layer and the surface of the convex pattern of the base metal layer are arranged on the same plane and formed on the convex pattern using the metal layer transfer base sheet. When transferring a transfer metal layer to a pressure sensitive adhesive sheet, there is a problem that the insulating layer on the electrodeposition substrate is subjected to peeling stress due to adhesive transfer, and the insulating layer is peeled off from the conductive base material after a few repeated uses. .
In addition, in Patent Document 2, a transfer metal layer formed on a convex pattern using a metal layer transfer base sheet in which the surface of the convex pattern made of an electroplated metal layer is formed higher than the surface of the electrical insulating layer. When transferring to the adhesive sheet, the transfer metal layer was also plated on the side of the convex pattern, which provided resistance to the adhesive transfer of the transfer metal layer, and the transfer metal layer could not be peeled off from the convex pattern or could be peeled off However, there is a problem that the mesh pattern is broken and the electromagnetic wave shielding property is deteriorated.
In Patent Document 2, a method for manufacturing a base sheet for transferring a metal layer includes forming an etching resist on the surface of the base metal layer and etching the surface of the base metal layer that is exposed without being covered with the etching resist. The number of processes is increased, and it cannot be said that the method is highly productive.

  The present invention firstly provides a conductive substrate for plating capable of more uniform plating, and provides a conductive substrate for plating that facilitates the preparation of such a conductive substrate for plating. A manufacturing method is provided. Second, the present invention can produce a patterned conductor layer pattern with high productivity, and can also produce a patterned substrate with a conductive layer pattern with high productivity using a transfer method. In addition, the present invention provides a conductive substrate for plating that is easy to produce and a method for producing the same. Third, the present invention relates to a method for producing a conductor layer pattern or a substrate with a conductor layer pattern using such a conductive substrate for plating, a substrate with a conductor layer pattern, and an electromagnetic wave shielding member using the same. Is to provide.

The present invention relates to the following.
1. A conductive base material for plating on which a conductive diamond-like carbon film or a conductive inorganic material film is formed.
2. A conductive substrate for plating comprising a substrate and a conductive diamond-like carbon film or a conductive inorganic material film formed on the surface of the substrate.
3. A conductive substrate for plating including a substrate and a conductive diamond-like carbon film formed on the surface of the substrate, wherein the conductive diamond-like carbon film is a hydrogen-free diamond-like carbon film 2. The electroconductive substrate for plating according to 2.
4). A conductive substrate for plating comprising a substrate and a conductive diamond-like carbon film formed on the surface of the substrate, wherein the conductive diamond-like carbon film contains impurities for imparting conductivity. Item 3. The electroconductive substrate for plating according to Item 2, which is a waste product.
5. Item 3. A conductive substrate for plating including a substrate and a conductive inorganic material film formed on a surface of the substrate, wherein the conductive inorganic material film is a chromium nitride film. Base material.
6). An intermediate layer containing at least one of Ti, Cr, W, Si, Ta, Nb, Zr, or a nitride or carbide thereof is interposed between the base material and the conductive diamond-like carbon film or the conductive inorganic material film. Item 6. The conductive substrate for plating according to any one of Items 2 to 5.
7). Item 7. The conductive substrate for plating according to any one of Items 2 to 6, wherein the surface of the substrate is made of steel, Ti, nickel-base alloy, chromium or nickel alloy plating or sprayed metal.
8). A conductive base material on which a conductive diamond-like carbon film or a conductive inorganic material film is formed, and an insulating layer formed on the surface of the conductive diamond-like carbon film or the conductive inorganic material film; A conductive base material for plating, wherein the insulating layer has a recess that is wide in the opening direction and is formed to form a plating.
9. Item 9. The conductive substrate for plating according to Item 8, wherein the conductive substrate includes a substrate and a conductive diamond-like carbon film or a conductive inorganic material film formed on the surface of the substrate.
10. Item 10. The conductive base material includes a base material and a conductive diamond-like carbon film formed on the surface of the base material, and the conductive diamond-like carbon film is a hydrogen-free diamond-like carbon film. Conductive base material for plating.
11. Item 10. The conductive base material includes a base material and a conductive diamond-like carbon film formed on the surface of the base material, and the conductive diamond-like carbon film includes an impurity imparting conductivity. Conductive base material for plating.
12 Item 10. The conductive substrate for plating according to Item 9, wherein the conductive substrate has a conductive inorganic material film formed of a chromium nitride film on the surface.
13. The conductive base material includes a base material and a conductive diamond-like carbon film formed on the surface of the base material, and Ti, Cr, W, Si, Ta are provided between the base material and the conductive diamond-like carbon film. Item 13. The conductive substrate for plating according to Item 9 to 12, wherein an intermediate layer containing any one or more of Nb, Zr, nitrides or carbides thereof is interposed.
14 Item 14. The conductive substrate for plating according to any one of Items 9 to 13, wherein the surface of the substrate is made of steel, Ti, nickel-base alloy, chromium or nickel alloy plating, or sprayed metal.
15. Item 15. The conductive substrate for plating according to any one of Items 8 to 14, wherein the recess for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself.
16. Item 16. The conductive substrate for plating according to any one of Items 8 to 15, wherein the minimum width of the recesses is 1 to 40 μm, the maximum width of the recesses is 2 to 60 μm, and the interval between the recesses is 50 to 1000 μm.
17. Item 17. The conductive substrate for plating according to any one of Items 8 to 16, wherein the side surface of the recess has an angle of 30 degrees or more and less than 90 degrees on the insulating layer side.
18. Item 18. The conductive substrate for plating according to any one of Items 8 to 17, wherein the insulating layer is made of diamond-like carbon or an inorganic material.
19. Item 18. The intermediate layer containing any one or more of Ti, Cr, W, Si, Zr, or a nitride or carbide thereof between the conductive substrate and the insulating layer. Conductive base material for plating.
20. (A) A convex surface that can be removed on the surface of the conductive diamond-like carbon film or conductive inorganic material film of the conductive base material on which the conductive diamond-like carbon film or conductive inorganic material film is formed. Forming a pattern;
(B) The process of forming the insulating layer which consists of diamond-like carbon or an inorganic material on the surface of the electroconductive base material in which the convex-shaped pattern which can be removed is formed, and (C) The convex shape which the insulating layer has adhered The manufacturing method of the electroconductive base material for plating characterized by including the process of removing the pattern of this.
21. Item 21. The method for producing a conductive substrate for plating according to Item 20, wherein the removable convex pattern is formed by a photolithography method using a photosensitive resist.
22. Item 20 or 21. The plating conductive material according to item 20 or 21, wherein the pattern shape of the removable convex portion has a width of 1 to 40 μm, a distance of 50 to 1000 μm, and a height of 1 to 30 μm, whereby a geometric figure is drawn. For producing a conductive substrate.
23. Item 23. The method for producing a conductive substrate for plating according to any one of Items 20 to 22, wherein the insulating layer is diamond-like carbon or an inorganic material.
24. Item 24. The method for producing a conductive substrate for plating according to any one of Items 20 to 23, wherein in the step of forming the insulating layer, an insulating film having different properties or characteristics is formed on the side surface of the convex pattern on the conductive substrate. .
25. Item 25. The conductive group for plating according to Item 24, wherein in the step of forming the insulating layer, the hardness of the diamond-like carbon film as the insulating layer to be formed is greater than the hardness of the diamond-like carbon film formed on the side surface of the convex pattern. A method of manufacturing the material.
26. The hardness of the diamond-like carbon film formed on the conductive substrate is 10 to 40 GPa, and the hardness of the diamond-like carbon film formed on the side surface of the convex pattern is 1 to 15 GPa. A method for producing a conductive substrate.
27. In the step of forming the insulating layer, the boundary surface between the insulating layer formed on the conductive substrate and the insulating layer formed on the side surface of the removable convex pattern faces the outside of the convex pattern as a whole. 27. A method for producing a conductive substrate for plating according to any one of Items 24 to 26, which is inclined.
28. Item 28. The method for producing a conductive substrate for plating according to Item 27, wherein the angle of the boundary surface is formed to be 30 degrees or more and less than 90 degrees with respect to the surface of the conductive substrate.
29. Item 29. The electroplating conductivity according to any one of Items 20 to 28, wherein the diamond-like carbon film as the insulating layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization deposition method, or a plasma CVD method. A method for producing a substrate.
30. Before performing the step of forming the insulating layer on the surface of the conductive substrate on which the removable convex pattern is formed, on the surface of the conductive substrate on which the removable convex pattern is formed Item 30. The method for producing a conductive substrate for plating according to any one of Items 20 to 29, wherein the step of forming an intermediate layer is performed.
31. Item 31. The method for producing a conductive substrate for plating according to Item 30, wherein the intermediate layer contains one or more of Ti, Cr, W, Si, Ta, Nb, Zr, or a nitride or carbide thereof.
32. (A) A step of depositing metal by plating in the concave portion of the conductive base material for plating according to any one of Items 8 to 19 and (B) a step of peeling the metal deposited in the concave portion of the conductive base material. A method for producing a conductor layer pattern, comprising:
33. (B) a step of depositing a metal by plating in the concave portion of the conductive base material for plating according to any one of Items 8 to 19, and (b) another base material with the metal deposited in the concave portion of the conductive base material. The manufacturing method of the base material with a conductor layer pattern characterized by including the process to transcribe into.
34. Item 34. The method for producing a substrate with a conductor layer pattern according to Item 33, wherein the thickness of the metal deposited by plating is not more than twice the depth of the recess.
35. Item 35. The method for producing a substrate with a conductor layer pattern according to Item 33 or 34, wherein the another substrate has an adhesive layer having at least adhesiveness on the surface.
36. Item 36. The method for producing a substrate with a conductor layer pattern according to any one of Items 33 to 35, comprising a step of blackening the metal deposited in the concave portion of the conductive substrate for plating.
37. Furthermore, the manufacturing method of the base material with a conductor layer pattern in any one of claim | item 33-36 including the process of blackening the metal pattern transcribe | transferred to another base material.
38. Item 38. A substrate with a conductor layer pattern, produced by the method according to any one of Items 33 to 37.
39. Item 39. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 38 with a resin.
40. Item 40. A light-transmitting electromagnetic wave shielding plate obtained by bonding the substrate with a conductor layer pattern according to Item 38 or the light-transmitting electromagnetic wave shielding member according to Item 39 to a transparent substrate.
Moreover, it is preferable that any of the above-described insulating layers is diamond-like carbon, Al ₂ O ₃ or SiO ₂ . In addition, any of the above-described insulating layers is preferably diamond-like carbon having a hardness of 10 to 40 GPa. Moreover, it is preferable that the thickness of any of the insulating layers described above is 0.5 to 20 μm. Further, any of the above-described conductive substrates for plating may be wound around a conductive roll (drum) or a roll.
In the step of forming the insulating layer, the angle of the boundary surface described above is preferably 30 degrees or more and 60 degrees or less with respect to the surface of the conductive base material. The angle is preferably 30 degrees or more and 60 degrees or less on the insulating layer side.

In the conductive substrate for plating of the present invention, by forming a conductive DLC film or a conductive inorganic material film on the surface of the substrate, correction of slight distortion on the substrate, repair of scratches, minute depressions, etc. And the surface can be made smoother. As a result, a more uniform metal foil can be produced regardless of whether it is patterned or not. As a result, when an insulating layer patterned on the surface of the conductive substrate is formed, the adhesion of the resist film used for that purpose can be improved, and the patterning can be made more precise and finer. I can plan.
Moreover, in the conductive base material for plating of the present invention, when the conductive base material for plating is repeatedly used by forming a conductive DLC film or a conductive inorganic material film on the base material, Modifications can be simplified or omitted. Further, the polishing or chemical treatment of the surface of the conductive base material, which has been required to be performed periodically, because the deterioration of the metal surface due to the plating chemical that has conventionally occurred when using metal as the conductive base material is reduced or eliminated. This makes maintenance work easier or unnecessary. Furthermore, it is possible to reduce the disadvantage that the metal surface of the conductive substrate is gradually peeled off during the transfer of the plated metal. As a result, the electroconductive substrate for plating can be provided at a low cost.
In addition, by forming a conductive DLC film or a conductive inorganic material film on the substrate, it is possible to easily or omit the inspection of the surface of the conductive substrate for scratches or dents.
The adhesion between the base material and the conductive DLC film or the conductive inorganic material film can be improved by the intermediate layer between the base material and the conductive DLC film or the conductive inorganic material film.

  In the conductive base material for plating of the present invention, when the concave portion where the metal layer is formed by plating is wide in the opening direction, the conductor layer pattern obtained by plating is peeled from the conductive base material for plating. Is easy. Moreover, the adhesiveness to an electroconductive base material is excellent by making the material of an insulating layer into DLC or an inorganic material, and the peeling resistance is excellent. The insulating layer can improve the adhesion between the conductive base material and the insulating layer by the intermediate layer, thereby further extending the life of the conductive base material for plating.

  According to the method for producing a conductive substrate for plating of the present invention, a convex pattern is formed on a conductive substrate, and after forming the insulating layer, the convex pattern to which the insulating layer is attached is removed. Since the concave portion can be produced by this, the number of steps is small, and a wide concave portion can be easily produced in the opening direction. Therefore, in particular, the insulating layer on the conductive substrate and the convex pattern If the boundary surface with the insulating layer formed on the side surface is inclined toward the outside of the convex pattern as a whole, it is possible to easily form a wide concave portion toward the opening direction, so that the conductivity for plating The substrate can be produced with high production efficiency.

  According to the method for producing a conductor layer pattern of the present invention, the conductor layer pattern obtained by plating can be easily peeled off from the conductive substrate for plating, so that a conductor layer pattern having a specific pattern can be easily produced, Moreover, the conductor layer pattern excellent in translucency, electromagnetic wave shielding property, or electroconductivity can be manufactured easily. Furthermore, such a conductor layer pattern can be manufactured with high production efficiency.

  According to the method for producing a substrate with a conductor layer pattern of the present invention, since the conductor layer pattern obtained by plating can be easily peeled off from the conductive substrate for plating, the substrate with a conductor layer pattern can be easily produced. Moreover, the base material with a conductor layer pattern excellent in electromagnetic wave shielding properties or conductivity can be easily produced. Furthermore, such a substrate with a conductor layer pattern can be produced with high production efficiency.

  The electromagnetic wave shielding member and the electromagnetic wave shielding plate in the present invention are excellent in light transmittance and electromagnetic wave shielding property by using a specific conductor layer pattern, and can be produced with high production efficiency.

The conductive substrate for plating in the present invention is a conductive substrate including a substrate and a conductive diamond-like carbon (DLC) film or a conductive inorganic material film formed on the surface of the substrate. Thus, the surface can be plated.
The degree of conductivity of the conductive DLC film or the conductive inorganic material film is preferably 1 × 10 ³ Ω · cm or less, more preferably 1 × 10 ² Ω · cm or less in terms of volume resistivity. The following are most preferred. The higher the electrical conductivity, the easier it is for the plating to deposit and the lower the volume resistivity. If it exceeds 1 × 10 ³ Ω · cm, the plating does not precipitate or the resistance value is high even if it is deposited, so that the voltage during plating tends to increase or heat generation tends to occur. When the volume resistivity is less than 1 × 10 ⁻⁶ Ω · cm, it tends to be difficult to produce the volume resistivity. When the conductivity of the conductive DLC film or the conductive inorganic material film is evaluated by volume resistivity, as will be described later, when an intermediate layer is provided below the conductive DLC film or the conductive inorganic material film, It is the value which laminated | stacked the film | membrane and measured these together.
The volume resistivity is measured by separately forming the conductive DLC film or conductive inorganic material film or an intermediate layer on an insulator such as silicon wafer or glass, and then forming the conductive DLC film or conductive inorganic material film on the intermediate layer. Can be measured by a four-end needle resistance measurement method (for example, Lorester GP, manufactured by Mitsubishi Chemical Corporation can be used as an apparatus). When the intermediate layer was used, the volume resistivity was calculated using the sum of the thickness of the intermediate layer and the thickness of the conductive DLC film or the conductive inorganic material film as the sample thickness.

  The electroconductive substrate for plating in the present invention is also an electroconductive substrate having a patterned plating portion, and an insulating layer is formed on the surface of the electroconductive substrate, and the insulating layer is formed in the opening direction. A concave portion (plating portion) for forming a wider plating is formed. The conductive material is exposed on the bottom surface of the recess. The conductive base material includes a base material and a conductive DLC film or a conductive inorganic material film formed on the surface of the base material.

  In this invention, an electroconductive base material has sufficient electroconductivity in order to deposit a metal by the electroplating to the plating part of the surface. The substrate having the conductive DLC film or the conductive inorganic material film on the surface thereof is particularly preferably a conductive substrate such as a metal. In addition, the conductive substrate for plating is preferably one that can easily peel off the metal layer formed by electrolytic plating on the surface of the plating part, and also so that it can be transferred to the adhesive support. It is preferable that the adhesive strength with the metal layer formed thereon is low and can be easily peeled off. The base material on which the conductive DLC film or the conductive inorganic material film is formed has a certain degree of resistance so that the corrosion resistance can be maintained even if there is a pinhole in the conductive DLC film or the conductive inorganic material film formed thereon. It is preferable that there is corrosion resistance. As the material for such a conductive base material, stainless steel, titanium, titanium alloy, titanium-lined material, nickel, nickel-base alloy, or the like can be used. Further, the corrosion-resistant layer can be formed by plating such as cast iron plated with chromium, steel plated with chromium, or steel plated with nickel alloy. Alternatively, cermet or cemented carbide can be formed by thermal spraying. When the conductive DLC film has sufficient conductivity, the substrate may be an insulator such as ceramic. More preferably, the substrate has corrosion resistance and high hardness.

  The method for forming the conductive DLC film or the conductive inorganic material film on the substrate is basically the same as the method for forming the insulating DLC film or the inorganic material film described below, but the DLC film or the inorganic material film is used. A method for imparting conductivity to the surface is taken into consideration.

Various methods can be used as a method for imparting conductivity to the DLC film. Some examples are listed below, but are not limited to the methods described below.
For example, the DLC film can be made conductive by mixing one or more impurities such as boron, nitrogen, and phosphorus in addition to carbon and hydrogen. When mixing impurities by the plasma CVD method, a DLC forming gas containing these impurities is mixed in the chamber to form a DLC film, whereby impurities (boron and nitrogen) are in the form of molecules or atoms in the DLC film. The film thus obtained is electrically conductive.
For example, diborane (B ₂ H ₂ ) or boron oxide (B ₂ O ₃ ) can be used as a boron source that is an impurity as a plasma CVD reaction gas used at that time. As the nitrogen source, for example, nitrogen (N ₂ ) can be used. Mixing these elements makes the DLC film conductive even though it uses hard carbon with electrical insulation, as is used as an impurity in the manufacture of semiconductors made of single crystals such as silicon. To do.

  In addition, the DLC film can be provided with conductivity by incorporating a substance (impurity) having conductivity in addition to the impurities into the film. For example, Ti (titanium), V (vanadium), Cr (chromium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Hf (hafnium), Ta (tantalum), W (tungsten), Au (gold) ), Pt (platinum), and Ag (silver), a conductive film can be obtained by adding at least one element selected from the film.

Increasing the amount of impurities added to lower the electrical resistivity tends to deteriorate characteristics such as wear resistance. As for the lower limit of the impurity addition amount, for example, in the case of tungsten (W) addition by the plasma CVD method, the electrical resistivity does not become 1 × 10 ⁶ Ω · cm or less unless 0.0001 atomic% or more is added. On the other hand, when Au is added by the ion implantation method, the electrical resistivity becomes 1 × 10 ⁶ Ω · cm or less even when 0.000001 atomic% is added. Thus, the lower limit of the electrical resistivity varies depending on the element and method to be added. Therefore, the lower limit of the impurity addition amount in the DLC film of the present invention is preferably 0.001 atomic% or less in consideration of each additive element.

As a method for adding impurities in forming the conductive DLC film of the present invention, the following method can be applied.
(A) A method in which a gas containing an impurity element is supplied to the reaction system and added to the film while forming the DLC film by a known method. This method is particularly effective in plasma CVD, sputtering, ion plating, laser ablation, and the like.
(B) A method of adding a solid source containing an impurity element to a film by heat evaporation, sputter evaporation, or ablation while forming a DLC film by a known method. This method is particularly effective in sputtering, ion plating, ion beam sputtering, laser ablation, and the like.
(C) A method of adding impurities into the film by irradiating an ion beam containing an impurity element during the formation of the DLC film by a known method.
(D) A method of adding impurities by implanting ions containing impurities after forming a DLC film by a known method.
(E) A method in which a DLC containing an impurity element is formed by flowing a gas serving as a reactive carbon source while sputtering a solid source containing the impurity element by a known method.
In forming the DLC film to which the impurities are added, the above method may be applied alone or a plurality of methods may be used in combination. Further, the above method and other methods may be used in combination.
When these impurity elements are added to the film, the density of the carbon amorphous network is increased by performing ion irradiation on the deposited DLC film at the same time as the film formation, and the additive elements are further clustered. And can be finely dispersed. Furthermore, by irradiating the amorphous carbon film with a low-energy electron beam after film formation, the macro is only applied to the periphery of the finely dispersed impurity element without changing the structure of the amorphous carbon network. Local ultrafine graphite clusters can be formed.
In addition, a DLC layer with a high content of sp3 orbits from a DLC layer with a high content of sp2 orbitals from a DLC layer with a high content of graphite components from a DLC layer with a high content of graphite components in a continuous or stepwise manner from the substrate side toward the upper layer in order from the substrate side. A conductive DLC film can be formed by depositing layers and forming a DLC film.

  As another method, there is also a method of imparting conductivity while applying a positive pulse by an ion implantation method using a pulse power source. In other words, by applying a negative high voltage pulse to a substrate placed in methane plasma, methane ion irradiation is performed from all directions of the substrate, and a high resistance layer such as an oxide film on the substrate surface is removed and ions are By the injection, a conductive film in which carbon atoms are dispersed is formed on the substrate surface. Next, hydrocarbons with a large molecular weight such as toluene are introduced into a vacuum chamber, these plasmas are generated by high frequency discharge, glow discharge, etc., and radicals are deposited, and a negative high voltage pulse is applied to the substrate, The substrate is irradiated with accelerated positive ions. At this time, by applying a positive high voltage pulse to the substrate and irradiating the substrate with electrons in the plasma, only the surface layer is activated in a pulsed manner and brought to a high temperature state to deposit hydrocarbon radicals and ions. . By organically combining these steps, a DLC film having high conductivity, high corrosion resistance, and high adhesion can be formed. Further, nitrogen may be mixed in the gas of the DLC film generation process.

Conversely, a hydrogen-free DLC film that does not mix impurities has conductivity. A hydrogen-free DLC film can be formed by sputtering or vacuum arc deposition, using carbon as a target or cathode material, and without forming an atmosphere gas serving as a hydrogen source such as methane or acetylene. Common hydrogen-free volume resistivity in DLC films that can be a sputtering method (specific resistance) is obtained films ^{10 0 ~1 × 10 5 Ω /} cm, conductivity by increasing the sp ² components in a vacuum arc deposition You can raise the nature.
Even if it is said hydrogen-free film | membrane, about several percent hydrogen may be contained in a film | membrane by the influence of the water | moisture content adsorb | sucked to the sputtering target, the base material, and the chamber inner wall, but it has required electroconductivity. Needless to say, it can be used as a conductive DLC film.

  The method for making the inorganic material conductive can also be performed in accordance with the method for making the DLC conductive. However, if it is a conductive inorganic material itself, the operation of imparting conductivity is not necessary. Inorganic conductive materials themselves include inorganic compounds such as titanium aluminum nitride, chromium nitride, titanium nitride, titanium nitride chromium, titanium carbonitride, and titanium carbide. These films can be formed by physical vapor deposition such as sputtering or ion plating or chemical vapor deposition such as plasma CVD. Among these, chromium nitride is particularly preferable because of its excellent chemical resistance. Chromium nitride can be formed by an ion plating method, a sputtering method, or the like. For example, when forming a film by sputtering, there are a method of forming a film as it is using chromium nitride as a target, and a method of forming a film by reactive sputtering while introducing nitrogen gas using chromium as a target, either of which can be applied. In reactive sputtering, the ratio of chromium to nitrogen does not become 1: 1, and a metal chromium component or the like may be included as it is, but even in that case, there is no problem in corrosion resistance and it can be used.

  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.

When the conductive base material for plating of the present invention is formed so that the concave portion in which the metal layer is formed by plating is widened in the opening direction, for example, the concave portion is formed on the surface of the conductive base material. It is formed using an insulating layer.
The thickness of the insulating layer corresponds to the depth of the recess. Since the depth of the recess is also related to the thickness of the deposited plating, it is appropriately determined according to the purpose. The thickness of the insulating layer is preferably in the range of 0.10 μm to 100 μm, and more preferably in the range of 0.5 μm to 10 μm. If the insulating layer is too thin, pinholes are likely to be generated in the insulating layer, so that when the plating is performed, the metal is likely to be deposited on the portion where the insulating layer is applied. The thickness of the insulating layer is particularly preferably 1 to 5 μm.

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

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

An example of the present invention will be described with reference to the drawings.
FIG. 1 is a partial perspective view showing an example of a conductive substrate for plating according to the present invention. FIG. 2 is a cross-sectional view taken along the line AA in FIG. FIG. 2A shows a case where the side surface of the recess is planar, while FIG. 2B shows a case where the side surface of the recess has gentle irregularities. In the conductive base material 1 for plating, an insulating layer 3 is laminated on a conductive base material 2, and a concave portion 4 that is a plating portion is formed on the insulating layer 3, and the bottom of the concave portion 4 is electrically conductive. The base material 2 is exposed. The bottom of the recess 4 may be a conductor layer that is electrically connected to the conductive substrate.
In this example, the insulating layer 3 has a square shape as a geometric figure, and a recess 4 is formed in a groove shape around the square.
A conductive or insulating intermediate layer (not shown) may be laminated between the conductive substrate 2 and the insulating layer 3 for the purpose of improving the adhesiveness of the insulating layer 3 or the like. Alternatively, the recess 4 is wide as a whole in the opening direction. It is not always necessary that the width is constant and wide at the gradient α as shown in the drawing. If there is no problem in peeling of the conductor layer pattern formed by plating, the recess may have a portion whose width becomes narrower in the opening direction, but it is better not to have such a portion, It is preferable that it is not narrowed toward the opening direction but spreads as a whole. In particular, it is preferable that one side surface of the concave portion together with the opposite surface thereof has no portion that is perpendicular to the bottom surface and continues in the height direction by 1 μm or more. If it is such a conductive substrate for plating, after plating using it, when peeling the deposited metal layer from the conductive substrate for plating, friction between the metal layer and the insulating layer or The resistance can be reduced, and the peeling becomes easier.

によってαを決定する。
αは、角度で３０度以上９０度未満が好ましく、３０度以上８０度以下がより好ましく、３０度以上６０度以下が特に好ましい。この角度が小さいと作製が困難となる傾向があり、大きいと凹部にめっきにより形成し得た金属層（導体層パターン）を剥離する際、又は、別の基材に転写する際の抵抗が大きくなる傾向がある。 The side surface of the recess is not necessarily a flat surface. In this case, as shown in FIG. 2 (b), the gradient α is such that the height h of the recess (this is the thickness of the insulating layer) and the width s of the side surface of the recess (in the horizontal direction). Width direction of the side surface of the recess)

Determines α.
α is preferably 30 ° or more and less than 90 °, more preferably 30 ° or more and 80 ° or less, and particularly preferably 30 ° or more and 60 ° or less. If this angle is small, the production tends to be difficult, and if it is large, the resistance when peeling the metal layer (conductor layer pattern) that can be formed by plating in the recess or transferring to another substrate is large. Tend to be.

The planar shape of the insulating layer and the thickness of the insulating layer or the depth of the recess in the conductive substrate for plating of the present invention are appropriately determined according to the use of the patterned metal obtained using the conductive substrate for plating of the present invention. Is done.
The concave portion of the conductive base material for plating corresponds to the shape of the patterned metal generated by plating, but also corresponds to the conductive layer pattern in the base material with a conductive layer pattern, and the conductive layer pattern is This corresponds to the electromagnetic wave shielding layer when the electromagnetic wave shielding member is finally produced.

  In addition, the thickness of the insulating layer is the same as described above. In order to correspond to this, the depth of the recess 4 in the conductive substrate for plating of the present invention is preferably 0.1 to 100 μm. 0.5 to 10 μm is more preferable, and 1 to 5 μm is particularly preferable.

When the conductive substrate for plating of the present invention is used to produce a light-transmitting electromagnetic wave shielding member by a transfer method, the width of the recess 4 as shown in FIG. It is preferable that the width d ′ at the bottom is 1 to 40 μm. The width d of the opening of the recess 4 is particularly preferably 4 to 15 μm, and the width d ′ of the bottom is particularly preferably 3 to 10 μm. The center interval (line pitch) of the recesses 4 is preferably 50 to 1000 μm, and particularly preferably 100 to 400 μm. The width of the groove and the interval between the grooves are determined considering that the opening ratio of the conductor layer pattern is preferably 50% or more, particularly preferably 80% or more.
In the plated part other than the concave part as described above, the width and the center interval of the plated part are preferably determined with reference to 1 to 40 μm and 50 to 1000 μm, respectively, and the opening ratio of the conductor layer pattern Is preferably 50% or more, particularly preferably 80% or more.
In the present invention, the center interval (line pitch) of the recesses cannot be easily determined because the figure pattern of the insulating layer formed by the recesses is a complicated figure or a combination of a plurality of figures. Is defined as the length of one side of the pattern by converting the area into a square area based on the repeating unit of the pattern.

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

When used to produce a perforated metal foil using the conductive substrate for plating of the present invention, the insulating layer 3 as shown in FIG. 2 has its bottom surface (contact surface with the conductive substrate). Is preferably 1 to 1 × 10 ⁶ square microns, and the distance between the insulating layers (the shortest distance between the protrusions) is preferably 1 to 1000 μm. The insulating layer 3 preferably has a bottom area of 1 × 10 ² to 1 × 10 ⁴ square microns, more preferably 10 to 100 μm. The area of the bottom surface of the insulating layer and the interval thereof are determined in consideration of the opening ratio of the conductor layer pattern being preferably 10% or more, particularly preferably 30% or more. Such a perforated metal foil is useful as a current collector of a capacitor.

The method for producing a conductive substrate for plating in the present invention includes a step of forming an insulating layer on the surface of the conductive substrate so that a geometrical figure is drawn by a recess exposing the conductive substrate. .
This step includes (A) a step of forming a removable convex pattern on the surface of the conductive substrate, (B) a surface of the conductive substrate on which the removable convex pattern is formed, A step of forming an insulating layer, and (C) a step of removing the convex pattern to which the insulating layer is attached.

For the step (A) of forming a removable convex pattern on the surface of the conductive substrate, a method of forming a resist pattern using a photolithographic method can be used.
This method
(A-1) forming a photosensitive resist layer on the conductive substrate;
(A-2) a step of exposing the photosensitive resist layer through a mask corresponding to the conductor layer pattern, and (a-3) a step of developing the exposed photosensitive resist layer.

Moreover, the step of forming a removable convex pattern on the surface of the conductive substrate (A),
(B-1) a step of forming a photosensitive resist layer on the conductive substrate;
(B-2) including a step of irradiating the photosensitive resist layer with a laser beam without masking a portion corresponding to the conductor layer pattern; and (b-3) a step of developing the photosensitive resist layer after the laser beam irradiation. .

  As the photosensitive resist, a well-known negative resist (a portion irradiated with light is cured) can be used. At this time, a negative mask (light passes through a portion corresponding to the concave portion) is also used as the mask. Further, a positive resist can be used as the photosensitive resist. Corresponding to these methods, the light irradiation part in the method a and method b is appropriately determined.

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

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

  In the above, it can carry out also by the method of using a thermosetting resin instead of a photosensitive resist, and removing the unnecessary part of a thermosetting resin by irradiation of a laser beam.

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

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

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

At this time, in the cross-sectional shape of the protrusion 6, the side surface is perpendicular to the conductive base material, or the end of the protrusion 6 is in contact with the end where the protrusion 6 contacts the conductive base 2. It is preferable to be in a position where at least a part of the upper side surface covers the end portion. In terms of the width of the protrusion 6, the maximum value d ₁ of the convex pattern width is preferably equal to or larger than the width d ₀ that contacts the convex pattern and the conductive substrate 2. This is because the concave width of the insulating layer having good adhesion is determined by d ₁ . Here, as a method of increasing the width d ₀ of the protrusion 6 in contact with the conductive substrate 2 in the cross-sectional shape of the protrusion 6, the maximum width d ₁ of the protrusion 6 is equal to or larger than the width d _0. A resist having a characteristic that sometimes over-develops or has an undercut shape may be used. d ₁ is preferably is realized at the top of the convex portion.
The shape of the protrusion 6 that forms the pattern of the removable convex portion is associated with the shape of the concave portion. From the ease of production, the maximum width is 1 μm or more, the interval is 1 μm or more, and the height is 1 to 50 μm. Preferably there is. When the conductive substrate for plating is used to produce a conductor layer pattern for a light-transmitting electromagnetic wave shielding member, the protrusion 6 has a maximum width of 1 to 40 μm, an interval of 50 to 1000 μm, and a height of 1 to 1. Each of 30 μm is preferable. In particular, it is preferable that the maximum width is 3 to 10 μm and the interval is 100 to 400 μm. Further, when the conductive substrate for plating is used for producing a perforated metal foil, the planar shape is a circular or rectangular shape having an appropriate size so that the insulating layer 3 as described above is formed. Are arranged at appropriate intervals.

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

  As a method for forming a DLC thin film as an insulating layer, a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, a physical vapor deposition method such as an ionization deposition method, a chemical vapor deposition method such as a plasma CVD method, etc. However, the plasma CVD method using a high frequency or pulse discharge in which the film forming temperature can be controlled from room temperature is particularly preferable.

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

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

The insulating layer may be formed entirely by the above-described insulating DLC thin film or inorganic material film, but improves the adhesion of the DLC thin film or inorganic material film to a conductive substrate such as a metal plate. In order to further improve the durability of the insulating layer, one or more components selected from Ti, Cr, W, Si, Ta, Nb, Zr, nitrides or carbides thereof, or the like may be used between them. It is preferable to interpose an intermediate layer.
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.

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

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

  In the formation of the insulating layer, the conductive base material does not become a shadow of the resist, and therefore the insulating layer on the conductive base material has uniform properties. On the other hand, the insulating layer is formed on the side surface of the convex pattern because the side surface of the convex pattern has an angle with respect to the film thickness direction on the conductive substrate. As for the film, an insulating layer having the same characteristics (for example, the same hardness) as the insulating layer on the conductive substrate cannot be obtained. In such a heterogeneous insulating layer contact surface, a boundary surface of the insulating layer is formed as the insulating layer grows, and the boundary surface is a growth surface of the insulating layer, and is smooth. For this reason, when the convex pattern consisting of the protrusions is removed, the insulating layer (particularly the DLC film) is easily separated at this boundary. Furthermore, the inclination angle α that becomes the boundary surface, that is, the side surface of the concave portion is that the growth of the insulating layer is delayed on the side surface of the protruding portion with respect to the film thickness direction on the conductive substrate. , Controlled as described above.

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. The insulating layer having a hardness of less than 10 GPa is soft, and when the conductive substrate is used as a plating plate, durability in repeated use is reduced. When the hardness is 40 GPa or more, it becomes impossible to follow the deformation of the base material when the conductive base material is processed such as bending, and the insulating layer is likely to be cracked or cracked. The hardness of the insulating layer formed on the conductive substrate is more preferably 12 to 30 GPa.
On the other hand, the hardness of the insulating layer formed on the side surface of the convex portion is preferably 1 to 15 GPa. The insulating layer formed on the side surface of the convex portion must be formed so as to be at least lower than the hardness of the insulating layer formed on the conductive substrate. By doing so, a boundary surface is formed between the two, and a wide concave portion is formed after a step of peeling the convex pattern composed of the protruding portion to which the insulating layer adheres later. The hardness of the insulating layer formed on the side surface of the protrusion is more preferably 1 to 10 GPa.

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

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

In this invention, the electroconductive base material in which a plating part consists of an electroconductive convex part pattern can also be used as an electroconductive base material for plating.
It is preferable that the width of the convex portion does not increase as the (exposed portion) advances in the tip direction, and that the width is smaller at the upper portion than at the lower portion as a whole. At this time, the concave portion corresponding to the convex portion is preferably covered with an insulating layer. Further, in this case, in the exposed portion of the convex portion, the end of the insulating layer on the side surface of the convex portion (first position) and the convex portion on the inner side in the width direction by an amount corresponding to 10% of the exposed width of the convex portion. The relationship d ₁₀ / h ₁₀ between the first position and the second position in the width direction d ₁₀ with respect to the distance h ₁₀ in the height direction from the surface position (second position) is 30 ° in angle. It preferably corresponds to ˜80 °. It is preferable that the width of the convex portion at a position 0.5 to 5 μm lower than the tip of the convex portion is 1 to 40 μm and the height of the convex portion exceeds 10 μm.

Examples of the method for forming the conductive protrusion on the conductive substrate include the following methods.
(1) Directly irradiate the laser beam to the part of the base material where the concave part is to be formed (the part corresponding to the opening of the conductive layer pattern of the base material with the conductive layer pattern) to form the concave part, corresponding to the conductor layer pattern A method of forming a raised protrusion,
(2) After performing a step of forming a geometrical figure shape pattern (resist pattern) on the base material with a photo-curable resin or a thermosetting resin by a photolithographic method or a printing method on the base material, Etching method,
(3) A method of excavating a portion (a portion corresponding to the opening of the conductor layer pattern of the substrate with the conductor layer pattern) where the concave portion of the substrate is to be formed by engraving. (4) A photolithographic method or a method on the conductive substrate. After performing a process of forming a geometrical pattern (resist pattern) on the conductive base material with a photocurable resin or thermosetting resin by printing, the resist pattern thickness is exposed on the exposed portion of the conductive base material. There is a method of forming a conductive convex pattern by plating thicker than that.
When the material of the substrate is hard, it is preferable to use the method (1) (laser processing method) or the method (2) (etching method) for direct processing, but it is soft and excellent in workability such as copper. When the material is used, it can be easily processed by the above method (3) (engraving method). At this time, after processing, a hard plating such as chromium can be applied to the surface to increase the strength.
In the above methods (1) to (3), a substrate in which a conductive film is formed on a conductive or non-conductive surface may be used. Alternatively, the conductive film may be formed on the surface after forming the convex portion by performing the above-described treatment using a conductive or non-conductive base material.

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 reverse printing, intaglio printing, letterpress offset printing, ink jet printing, flexographic printing, and the like can be used. As the resist, a photocurable or thermosetting resin can be used.
In the case of 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 may be subjected to an etching process after being exposed by wearing a mask 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 a plate is large or when it is produced by roll-to-roll (Roll-to-Roll), etc. 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.
Moreover, the etching of the base material in the method (2) can be performed using an etching solution. There are various types of etching solutions depending on the material of the substrate, and when etching solutions are commercially available for the respective substrates, they can be used. For example, if the base material is stainless steel, it is common to use ferric chloride, and if it is titanium, a hydrofluoric acid-based etching solution is often used. For 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 is large, so that 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. Further, if the etching temperature is low, the etching speed is lowered and the productivity is lowered. Therefore, the etching temperature is preferably 40 ° C. or higher. 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.
The remaining resist can be stripped using a stripping solution or the like after etching the substrate.

As a method for forming the insulating layer in the recess, for example, there is the following method.
Next, an adhesive film or the like that can be peeled off is attached and protected on one surface of the conductive substrate, and the whole surface of the etched surface is covered with an insulating layer. Thereafter, a mask layer for plasma etching is formed on the insulating layer.
As the insulating material for the insulating layer, a material having high adhesion to the conductive base material and strong chemical resistance is preferably used. In the step of electroplating or electroless plating, a material strong against both acid resistance and alkali resistance is particularly preferable because it is immersed in a pretreatment solution or a plating solution. As the insulating material, the aforementioned DLC can be used. The intermediate layer described above may be interposed between the DLC film and the conductive substrate.
Insulating materials and thermosetting resins such as 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 Resins, phenol resins, formalin resins, metal oxides, metal chlorides, oximes, alkylphenol resins, and the like can be used, but these are self-curing (a curing catalyst may be used).
As a thermosetting resin, a resin that has a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an unsaturated hydrocarbon group, and an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group are used. Some are used in combination with a curing agent having a functional group such as a group or a thiol group or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide, or peroxide. For the purpose of increasing the curing reaction rate, a general-purpose additive such as a catalyst can also 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 an insulating layer using a thermosetting resin include brush coating, spray coating, and further, a method of scraping the resin with a squeegee or blade after dipping and drying.
As the insulating material, an electrodeposition coating material may be used because the film is uniform, easy to form, and less burdensome on the environment. The electrodeposition paint can be used in any known cationic type or anionic type.

  Since the insulating layer is not etched at the portion where the mask layer is formed, the mask layer on the insulating layer formed at the tip of the convex portion of the conductive substrate is removed. This partial removal of the mask layer is removed in consideration of the width of the tip portion exposed by the convex portion. When the convex portion has a planar or substantially planar upper surface, it is preferable that the width of the exposed insulating layer be the same as or wider than the width of the upper surface.

Next, by performing dry etching on the insulating layer, the insulating layer formed at the tip portion of the convex portion can be removed, and thereby the tip portion of the convex portion can be exposed.
In particular, when plasma etching is performed with oxygen gas, when the surface of the conductive substrate is an inorganic material film, this becomes a stopper layer. When the convex part has a planar or substantially planar upper surface, if the insulating layer in the part exceeding the width of the upper surface of the convex part is exposed from the mask layer, the insulating layer can be removed by dry etching. Up to the side surface of the projection, and as a result, some of the side surface of the convex portion can be exposed. The removal of the insulating layer on the side surface can be controlled by the dry etching time and output.
Next, the mask layer formed on the insulating layer in the recess is removed by chemical immersion or the like. Thus, the electroconductive base material for plating which a plating part consists of a convex part pattern can be produced.

The mask layer can be broadly classified into inorganic and organic mask layers.
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 oxides of various metals by a dry coating method. As a coating method, it can be produced by 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.

In the present invention, the substrate with a conductor layer pattern is, for example,
(B) including a step of depositing a metal on the plating portion of the conductive base material for plating by plating, and (b) a step of transferring the metal deposited on the plating portion of the conductive base material to another base material. Manufactured by the method.

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

Next, the electroless plating will be further described. Typical examples of the electroless plating method include copper plating, nickel plating, tin plating, gold plating, silver plating, cobalt plating, iron plating, and the like. In the process of electroless plating used industrially, a reducing agent is added to a plating solution, and electrons generated by the oxidation reaction are used for a metal precipitation reaction. , Reducing agent, pH adjusting agent, pH buffering material, stabilizer and the like. In the case of electroless copper plating, copper sulfate is preferably used as the metal salt, formalin as the reducing agent, and Rossel salt or ethylenediaminetetraacetic acid (EDTA) as the complexing agent. Moreover, although pH is mainly adjusted with sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be used, carbonate and phosphate are used as a buffer, and monovalent as a stabilizer. Cyanide, thiourea, bipyridyl, O-phenanthroline, neocuproine, etc. that complex preferentially with copper are used. In the case of electroless nickel plating, nickel sulfate is preferably used as the metal salt, and sodium hypophosphite, hydrazine, a borohydride compound, or the like is preferably used as the reducing agent. When sodium hypophosphite is used, phosphorus is contained in the plating film, and the corrosion resistance and wear resistance are excellent. Moreover, as a buffering agent, a monocarboxylic acid or its alkali metal salt is often used. As the complexing agent, those that form a stable soluble complex with nickel ions in the plating solution are used, and acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycine, alanine, EDTA, etc. are used. In this case, sulfur compounds and lead ions are added. For the electroless plating method, pages 505 to 545 of Non-Patent Document 1 can be referred to.
Furthermore, in order to obtain the reducing action of the reducing agent, it may be necessary to activate the catalyst on the metal surface. When the substrate is a metal such as iron, steel, nickel, etc., these metals have catalytic activity, so they are deposited just by immersing them in the electroless plating solution, but copper, silver, their alloys, and stainless steel are used as the substrate. In this case, in order to impart catalyst activation, a method is used in which the object to be plated is immersed in an acidic hydrochloric acid solution of palladium chloride and palladium is deposited on the surface by ion substitution.

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

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

  The thickness (plating thickness) of the metal layer formed by plating on the plating portion of the conductive substrate is appropriately determined according to the purpose. The plating thickness is preferably 0.5 μm or more in order to exhibit sufficient conductivity (at this time, sufficient electromagnetic shielding properties are exhibited), and pinholes are formed in the conductor layer (at this time, For example, the thickness is more preferably 3 μm or more in order to reduce the possibility that the electromagnetic wave shielding property is reduced). If the plating thickness is too large, the formed metal layer also spreads in the width direction. This is also adjusted appropriately according to the purpose. Thus, when the plating thickness is too large, the line width becomes wide, and when the resulting metal layer is used for the electromagnetic wave shielding layer, the aperture ratio is lowered, and the transparency and invisibility of the electromagnetic wave shielding member are lowered. There is a tendency to make it. Therefore, in order to ensure sufficient transparency and invisibility as an electromagnetic wave shielding member, the thickness of the formed metal layer is preferably 20 μm or less, and further, the plating time is shortened and the production efficiency is improved. In order to increase the thickness, the thickness of the plating is more preferably 10 μm or less.

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

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

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

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

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

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

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

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

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

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

  The line width of the finally obtained conductor layer pattern of the substrate with a conductor layer pattern (meaning the conductor layer pattern blackened when the metal pattern is blackened) is 40 μm or less, and the line interval is 50 μm or more. It is preferable to set it as the range. 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 inferior, so 1 μm or more is preferable. The larger the line spacing, the better the aperture ratio and the visible light transmittance.

  In addition, when the substrate with a conductor layer pattern obtained by the present invention is used for a display front application, the aperture ratio of the portion that bears the electromagnetic wave shielding function is required to be 50% or more from the viewpoint of visible light transmittance. 60% or more is preferable, and 80% or more is particularly preferable. If the aperture ratio is too large, the line width becomes too small. Therefore, the aperture ratio is preferably 97% or less. From the viewpoint of the line interval, the line interval is preferably 1000 μm (1 mm) or less. If the line spacing becomes too large, the electromagnetic wave shielding property tends to decrease. When the line interval is complicated by a combination of geometric figures or the like, the area is converted into a square area with the repetition unit as a reference, and the length of one side is set as the line interval. From the viewpoint of visible light transmittance, the line interval is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 120 μm or more. The larger the line spacing, the better the aperture ratio and the visible light transmittance.

  Further, the thickness of the conductor layer pattern is preferably 100 μm or less, and when applied as an electromagnetic wave shielding sheet on the front surface of the display, the thinner the thickness, the wider the viewing angle of the display and the more preferable as an electromagnetic wave shielding material. Therefore, it is more preferably 40 μm or less, and further 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.

  When the plating part is a concave part, it is formed by plating from the viewpoint that the concave part becomes deeper relative to the thickness of the deposited metal layer, so that the deposited metal layer can be more shaped. The thickness of the metal foil 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, but is not limited thereto. Absent. In addition, 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 further, the surface of the concave side surface formed by the insulating layer can be smoothed, so that the anchor effect at the time of peeling of the metal foil pattern is reduced. it can. 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.

The example of preparation of the base material with a conductor layer pattern using said electroconductive base material for plating is shown next.
FIG. 5 is a cross-sectional view showing the first half of a production example of a base material with a conductor layer pattern. FIG. 6 is a cross-sectional view showing the latter half.
On the conductive base material 1 for plating, plating is performed in the recess 4 which is a plating portion by the above-described plating step, thereby forming a conductor layer pattern 9 (FIG. 5E). Next, a transfer substrate 10 prepared separately, which is a substrate (transparent substrate) 11 and a pressure-sensitive adhesive layer 12 laminated thereon. Preparation for pressure-bonding the transfer substrate 10 with the adhesive layer 12 facing the conductive substrate 1 for plating on which the conductor layer pattern 8 is formed is performed (FIG. 5F).
Next, the transfer substrate 9 is pressure-bonded to the conductive substrate 1 for plating on which the conductor layer pattern is formed with the adhesive layer 12 facing (FIG. 6G). At this time, the pressure-sensitive adhesive layer 12 may contact the insulating layer 7.
Next, when the transfer base material 10 is peeled off, the conductor layer pattern 9 adheres to the pressure-sensitive adhesive layer 12 and is peeled off from the concave portion 4 which is a plating portion of the plating conductive base material 1. As a result, the conductor layer pattern The attached base material 13 is obtained (FIG. 6H).

FIG. 7 is a cross-sectional view showing a state in which a conductor layer pattern is formed by plating in the concave portion of the conductive base material for plating, and FIG. 8 is with a conductor layer pattern obtained by transferring the conductor layer pattern in the concave portion. Sectional drawing of a base material is shown.
Since plating grows isotropically when plating on a conductive substrate for plating, the deposition of plating that started from the exposed portion of the conductive substrate overflows from the recess and covers the insulating layer as it progresses. To protrude and precipitate. From the viewpoint of sticking to the transfer substrate, it is preferable to deposit the plating so as to protrude. However, at this time, the plating may be deposited so as to be contained in the recess 4. This state is shown in FIG. Even in this case, as shown in FIG. 8, the conductor layer pattern 9 is transferred to the pressure-sensitive adhesive layer 12 by pressing the transfer substrate, and the conductor layer pattern 9 is peeled off from the conductive substrate 1 for plating. And the base material 13 with a conductor layer pattern can be produced.

The conductor layer pattern of the substrate with a conductor layer pattern obtained by the present invention can be blackened to obtain a substrate with a conductor layer pattern having a conductor layer pattern that has been blackened. For this purpose, a method of blackening the conductor layer pattern 9 of the substrate 13 with the conductor layer pattern as shown in FIG. 6 (h) or FIG. 8, a recess which is a plating portion of the conductive substrate 1 for plating. There are a method of blackening the conductive layer pattern 9 formed in 4 before it is transferred and a method of performing both blackening treatments.
When a substrate with a conductor layer pattern having a conductor layer pattern thus blackened is used as an electromagnetic wave shielding member on the front surface of the display, generally, the surface on which the black layer is provided is on the viewer side of the display. Used to face.

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

  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. 9 shows a cross-sectional view of an electromagnetic wave shielding member obtained by sticking a base material with a conductor layer pattern to another base material. In FIG. 9, a conductor layer pattern 9 made of metal is pasted on an adhesive layer 12 laminated on a base material (another base material) 11, and another base material 13 is laminated thereon, The conductor layer pattern 9 is embedded in the pressure-sensitive adhesive layer 12. This can be produced by pressing the conductor layer pattern 9 side of the substrate with the conductor layer pattern to the other substrate 13 under heating or non-heating. In this case, the conductor layer pattern is embedded in the pressure-sensitive adhesive layer 12 by applying an appropriate pressure while the pressure-sensitive adhesive layer 12 has sufficient fluidity or sufficient fluidity. As the base material (another base material) 11 and the base material (another base material) 13, an electromagnetic wave shielding member having high transparency can be obtained by using a material having transparency and excellent surface smoothness. Obtainable.
FIG. 10 shows a cross-sectional view of an electromagnetic wave shielding member in which a substrate with a conductor layer pattern is covered with a protective resin. A conductor layer pattern 9 made of metal is attached on a pressure-sensitive adhesive layer 12 laminated on a base material (another base material) 11, and these are covered with a transparent protective resin 14.

FIG. 11 is 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 in FIG. 10 is a surface opposite to the surface on which the conductive layer pattern 9 of the base material 11 is provided, and another base material 16 is bonded via an adhesive layer 15. is there.
FIG. 12 further shows a cross-sectional view of another embodiment of the electromagnetic wave shielding body. In FIG. 11, a conductor layer pattern 9 made of metal is bonded to a base material (another base material) 11 via a pressure-sensitive adhesive layer 12, and is coated with an adhesive or pressure-sensitive adhesive 17 made of a transparent resin. Further, a protective film 18 is laminated thereon. Another base material 16 such as a glass plate is attached to the other surface of the base material 11 via an adhesive layer 15. In this electromagnetic wave shielding member, the surface on which the conductor layer pattern 9 of the substrate with the conductor layer pattern having the conductor layer pattern 9 adhered to the substrate (another substrate) 11 via the adhesive 12 is transparent Then, a protective film 18 is laminated, and then an adhesive is applied to the other surface (the surface on which nothing is laminated) of the substrate 11 of the obtained laminate. Thus, the adhesive layer 12 can be formed and pressed against another substrate 16 for adhesion. As said transparent resin 17, the adhesive agent or adhesive which has as a main component the resin hardened | cured with an active energy ray other than a thermoplastic resin and a thermosetting resin can also be used. It is preferable to use a resin that cures with an active energy ray because it cures instantaneously or in a short period of time, resulting in an increase in productivity.

  In addition, as described above, a rotating body (roll) can be used as the conductive base material used in the present invention, and further details thereof will be described. The rotating body (roll) is preferably made of metal. Furthermore, it is preferable to use a drum electrode or the like used in the drum-type electrolytic deposition method as the rotating body. As described above, the material that forms the surface of the drum electrode is a conductive DLC or conductive inorganic material film on the outermost surface, and the underlying material is stainless steel, titanium, titanium alloy, titanium-lined material, nickel , Nickel base alloys, and the like can be used. Further, the corrosion-resistant layer can be formed by plating such as cast iron plated with chromium, steel plated with chromium, or steel plated with nickel alloy. Alternatively, cermet or cemented carbide can be formed by thermal spraying. By using a rotating body as the conductive base material, it is possible to obtain a base material with a conductor layer pattern as a roll, and in this case, productivity is greatly increased.

  A process of obtaining a structure as a scroll while continuously peeling a pattern formed by electroplating using a rotating body will be described with reference to FIG. FIG. 13 shows the concept of an apparatus for continuously depositing metal by electroplating while continuously rotating the drum electrode when using a drum electrode as the conductive substrate, and continuously stripping the deposited metal. It is sectional drawing (partial front view) shown.

  That is, the electrolytic solution 101 in the electrolytic bath 100 is supplied to the space between the anode 102 and the rotating body 103 such as a drum electrode by the pipe 104 and the pump 105. When a voltage is applied between the anode 102 and the rotator 103 and the rotator 103 is rotated at a constant speed, metal is electrolytically deposited on the surface of the rotator 103, and the conductivity of the surface of the rotator 103 is outside the electrolytic solution 101. The adhesive layer of the film 107 on which the adhesive layer is formed is pressure-bonded to the metal 106 deposited in the concave portion of the film by the pressure roll 108, and the metal 106 is formed on the film 107 on which the adhesive layer is formed while continuously peeling the metal 106 from the rotating body 103. 106 is transferred to form a substrate 109 with a conductor layer pattern. This can be wound up on a roll (not shown). Thus, the base material 109 with a conductor layer pattern can be manufactured. In addition, a concave portion and an insulating layer having a geometrical shape drawn thereby are formed on the surface of the rotating body 103. Further, the surface of the rotating body 103 may be etched and cleaned (not shown) after the metal 106 deposited in the concave portion is peeled off from the rotating rotating body 103 and before being immersed in the electrolytic solution 101. . Although not shown, a draining roll may be installed at the upper end of the anode 102 in order to prevent the electrolyte circulating at high speed from being ejected upward. The electrolyte stopped by the draining roll is the anode 102. Return to the bottom electrolyte bath from outside and circulated by the pump. Further, although not shown, it is preferable to add a mode in which a copper ion source and additives consumed during the circulation are added as necessary.

Furthermore, as described above, a hoop-like conductive base material can be used as the conductive base material used in the present invention.
The hoop-like conductive base material can be produced by forming an insulating layer and a recess on the surface of the belt-like conductive base material and then joining the end portions. As described above, the material forming the surface of the drum electrode is a conductive DLC or conductive inorganic material film on the outermost surface, and the underlying material is stainless steel, titanium, titanium alloy, titanium-lined material, nickel , Nickel base alloys, and the like can be used. Further, the corrosion-resistant layer can be formed by plating of cast iron plated with chromium, steel plated with chromium, steel plated with nickel alloy, or the like. Alternatively, cermet or cemented carbide can be formed by thermal spraying. When a hoop-like conductive base material is used, the process of blackening treatment, rust prevention treatment, transfer, etc. can be processed in one continuous process, so the productivity of the base material with a conductive pattern is high. Moreover, the base material with an electroconductive pattern can be produced continuously, and it can be set as a product as a scroll. The thickness of the hoop-like conductive substrate may be determined as appropriate, but is preferably 100 to 1000 μm.

  A process of obtaining a structure as a scroll while continuously peeling a conductor layer pattern formed by electroplating using a hoop-like conductive substrate will be described with reference to FIG. FIG. 14 is a conceptual diagram of an apparatus that peels while continuously depositing a conductor layer pattern by electroplating when a hoop-like conductive substrate is used as the conductive substrate.

  The hoop-shaped conductive substrate 110 is pre-treated tank 129, plating tank 130, washing tank 131, blackening tank 132, washing tank 133, rust prevention tank 134, washing tank 135 using transport rolls 111 to 128. Set up to move around in order. In the pretreatment tank 129, pretreatment such as degreasing or acid treatment of the conductive substrate 110 is performed. Thereafter, a metal is deposited on the conductive substrate 110 in the plating tank 130. Thereafter, the water washing tank 131, the blackening treatment tank 132, the water washing tank 133, the rust prevention treatment tank 134, and the water washing tank 135 are sequentially passed through, and the surface of the metal deposited on the conductive substrate 110 is blackened. Further rust prevention treatment. Although only one tank is shown in the figure after each treatment process, a plurality of tanks may be used as needed, or other pretreatment tanks may be provided before each treatment process. Next, the plastic film substrate 136 laminated with the adhesive layer is moved between the conductive substrate 110 and the pressure roll 137 on the transport roll 128 so that the metal deposited on the conductive recesses of the conductive substrate 110 is transferred. Then, the metal can be transferred to the plastic film substrate 136 to continuously manufacture the substrate 138 with a conductor layer pattern. The obtained base material 138 with a conductor layer pattern can be wound into a roll. If necessary, the pressure-bonding roll 137 can be heated, and although not shown, the plastic film substrate 136 may be preheated through a preheating tank before passing through the pressure-bonding roll. In addition, release PET or the like may be inserted as needed for winding the transferred film. Furthermore, after the metal is transferred, the hoop-like conductive base material repeats the above steps. Thus, the base material with a conductor layer pattern can be manufactured continuously with high productivity.

  When the substrate with a conductor layer pattern obtained as described above is used as an electromagnetic wave shielding member, 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 conductive base material may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer. Furthermore, a cover film (for example, the protective film 18 in FIG. 12) used when forming a protective layer on the conductor layer pattern may also serve as functional layers such as an antireflection layer and a near infrared shielding layer.

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

  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.

The electroconductive support for plating described in detail above has a concave pattern wide in the opening direction and an insulating layer corresponding to the pattern, and is produced with an appropriate width. When producing a conductor layer pattern required for the electromagnetic wave shielding member, if the area is defined as area A, the conductive substrate for plating according to the present invention includes an area (area) corresponding to the ground portion of the electromagnetic wave shielding member. B)). Region A and region B may have the same conductor layer pattern. In addition, the area ratio of the insulating layer in the region A (the ratio of the area of the portion excluding the recess when viewed in a plan view) may be larger than the area ratio of the insulating layer in the region B. , Preferably, it may be increased by 10% or more. The insulating layer ratio in the region B may be 0. In this case, a solid metal film is formed around the conductive support for plating by plating. Since the solid metal film is easily broken during transfer, the area ratio of the insulating layer in the region B is preferably 40% or more, and preferably less than 97%.
In the region B, as the geometric diagram shape drawn by the pattern of the recesses,
(1) Mesh-like geometric pattern (2) Square geometric pattern regularly arranged at predetermined intervals (3) Parallelogram pattern regularly arranged at predetermined intervals (4) Circular pattern or ellipse Pattern (5) Triangular pattern (6) Polygonal pattern of pentagon or more (7) Star pattern etc.
In addition, the formation of the plating portion, the formation of the insulating layer, and the like in the region B can be performed in the same manner as the region A described above. Further, it is preferable that the depth or height of the plated portion and the plated portion is a concave portion that the concave portion is wide in the opening direction as in the region A.

  Further, the thickness of the line of the conductor layer pattern at the portion that bears the grounding function is similarly preferably 0.5 μm or more, and more preferably 1 μm or more in order to ensure sufficient electric resistance. In addition, if there is a large difference between the conductor layer pattern line thickness of the part that performs the electromagnetic wave shielding function, a step will occur during transfer, and the boundary part will not be transferred or folds are likely to occur. The difference from the line thickness of the conductor layer pattern at the portion that performs the electromagnetic wave shielding function is preferably 10 μm or less, more preferably 5 μm or less.

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

A patterned metal foil can be produced by the following method.
(A) a step of depositing metal on the surface of the electroconductive substrate for plating by plating;
After this,
(B) A method for producing a patterned metal foil, comprising a step of peeling the metal deposited on the surface of the conductive substrate.
Here, the conductive base material for plating and the method for depositing metal by plating on the surface thereof are as described above.

  In the method for producing a substrate with a conductor layer pattern, another substrate used for transfer is used as an adhesive film for peeling, and is used for peeling the metal deposited on the plated portion of the conductive substrate, The transferred conductor layer pattern may be further peeled from this other substrate and used as a patterned metal foil.

  Moreover, in the manufacturing method of the base material with a conductor layer pattern described above, (b) instead of the step of transferring the metal deposited on the plated portion of the conductive base material to another base material (b ') A conductor layer pattern (patterned metal foil) can be produced by using the metal deposited on the plated portion of the conductive substrate as a step of peeling itself without using an adhesive film.

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

FIG. 15 is a bottom view showing a part of a perforated metal foil which is an example of a patterned metal foil. In the figure, six pairs of circles each composed of three concentric circles are drawn, and these are repeated in a zigzag manner at an appropriate number of times in the horizontal and vertical directions. FIG. 16 shows a cross-sectional view corresponding to the BB ′ cross-section in FIG. 15, and FIG. 16 shows a state in which the patterned metal foil is present on the conductive substrate for plating.
A hole 20 penetrates the patterned metal foil 19. Around the hole 20, there is a stepped portion 21 and an inclined portion 22 having a small width following the stepped portion 21. The stepped portion 21 and the inclined portion 22 correspond to the insulating layer 3 on the conductive base material 2 and the concave portion that is the plated portion on the conductive base material 2 formed thereby. The insulating layer 3 is formed so as to correspond to the end-sloped inclined portion. That is, in FIG. 16, the inclined portion 22 has an inner periphery (minimum diameter) and an outer periphery (maximum diameter), but the inclined portion 22 is inclined toward the outer periphery having a large diameter from the small inner periphery (the end of the stepped portion 21). is doing. The step portion 21 corresponds to a portion formed so that plating covers the insulating layer 3 from the concave portion of the conductive base material for plating. Therefore, since the thickness of the patterned metal foil 19 in the stepped portion 21 is a portion formed so as to cover the insulating layer 3, the portion closer to the hole 20 has a smaller thickness. It becomes higher by the thickness of the insulating layer 3 than the bottom surface of the patterned metal foil corresponding to the concave portion which is the plating portion.

  FIG. 17 is a cross-sectional view showing another example of the patterned metal foil, and shows a state existing on the conductive substrate for plating as in FIG. The plating deposited in the concave portion, which is the plating portion on the conductive substrate 2, grows on the insulating layer 3 and has no through hole, but has a patterned metal foil 19 having a concave portion corresponding to the insulating layer 3. It becomes. By extending the insulating layer 3 in the front and back direction of the paper and reducing the width, fine grooves can be formed in the patterned metal foil. By closing the groove with an appropriate material so that the inside is not filled, a fine liquid or gas flow path can be easily formed. Accordingly, the present invention can be applied to a heat sink, a supply channel for a small amount of drug, and the like. In addition, as said appropriate material, flat metal foil without a groove | channel or a recessed part, said patterned metal foil itself (The groove | channel is opposed, or the surface which passes a groove | channel is opposed, but a groove | channel does not overlap. A plurality of the patterned metal foils may be laminated in the same direction, and the surface including the last exposed groove can be closed with an appropriate material.

  After plating using the conductive substrate for plating, the patterned metal foil can be obtained by peeling the patterned metal foil formed on the substrate. In this case, as the substrate for peeling, a substrate in which an adhesive layer is laminated on another substrate is used, and the adhesive is applied to the metal foil surface of the plating conductive substrate on which the patterned metal foil is formed. To the contrary, after the base material for peeling is pressure-bonded, it is peeled off, the patterned metal foil is transferred to the base material for peeling, and the patterned metal foil can be peeled from the electroconductive substrate for plating. The patterned metal foil is appropriately obtained by peeling from the peeling substrate. Moreover, a patterned metal foil can be produced using the apparatus as shown in FIGS. In this case, the produced patterned metal foil may be peeled directly from the conductive substrate for plating without using the films 107 and 136, and the patterned metal foil is removed from the conductive substrate for plating. A peeling film (which itself is finally peeled from the patterned metal foil) may be used.

(Formation of conductive DLC film)
A conductive DLC film was formed using a coating apparatus (manufactured by HAUSER, HTC1500) having both a gas introduction tube and a sputtering target in the apparatus. Specifically, a 100 mm square stainless steel substrate (SUS304, mirror finish, thickness 0.5 mm, manufactured by Nisshin Steel Co., Ltd., hereinafter referred to as a substrate) is placed in a vacuum chamber, and plasma is first excited by Ar gas to clean the substrate. After the above, 0.2 μm of Cr was formed on one side of the substrate as an intermediate layer by sputtering. Next, while introducing acetylene gas and methane gas, tungsten carbide (WC) was sputtered, and DLC containing 10% tungsten (W) on the intermediate layer so that the film thickness was 1.5 to 2.5 μm. A layer was formed.

(Formation of convex pattern)
A resist film (Photech RY3315, 10 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to the surface of the substrate obtained above where the conductive DLC was formed. The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the line width of the light transmission part is 40 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square). Then, the negative film in which the pattern was formed in a lattice shape with a size of 80 mm square was left on the surface of the substrate on which the conductive DLC was formed. Using a UV irradiation device, a negative film was placed under a vacuum of 600 mmHg or less, and UV irradiation was performed at 120 mJ / cm ² from above the substrate. further. By developing with a 1% sodium carbonate aqueous solution, a lattice pattern consisting of a protrusion resist film (protrusion; height 10 μm) having a line width of 39 to 41 μm, a line pitch of 300 μm, and a bias angle of 45 degrees is formed on the conductive DLC. Formed.

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

(Concavity formation; removal of convex pattern with insulating layer attached)
The substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional shaking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 5 to 6 μm. Moreover, the width | variety in the bottom part of a recessed part was 39-41 micrometers, and the width | variety (maximum width) in an opening part was 49-53 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, an electrolytic bath (copper sulfate (pentahydrate) 250 g / L, sulfuric acid 70 g / L, sulfuric acid 70 g / L, cube) using the conductive substrate for plating obtained above as a cathode and phosphorus-containing copper as an anode. light AR (Ebara-Udylite Co., additive) solution of 4 ml / L, immersed in 30 ° C.), a current density over voltage as 10A / dm ² in both electrodes, the recess of the plating conductive substrate Plating was performed until the deposited metal thickness was approximately 7 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

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

(Transcription)
The surface of the pressure-sensitive adhesive layer of the transfer pressure-sensitive adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern of line width 63-69 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness (maximum) 7-8 micrometers was obtained. The shape of the conductor layer was wide from the lower part to the upper part (adhesive layer), reflecting the shape of the concave part, and the part overflowing from the concave part spread like an umbrella. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off. The line width and conductor layer thickness were measured by partially cutting out the obtained base material with a conductor layer pattern and casting it with a resin, and observing the cross section with a magnification of 3000 times by SEM. Since the measurement points were 5 and both sides of the recess were measured, the maximum and minimum values of 10 points in total were adopted (the same applies below). The line pitch was measured with a microscope (digital microscope VHX-500, manufactured by Keyence Corporation) at a magnification of 200 times, and the measurement was performed at five random points.

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

(Repeated use)
Next, as a result of repeating the copper plating-transfer process 500 times in the same manner as described above using the above-described conductive substrate for plating, there was no change in the precipitation and transferability of the copper plating, and the insulating layer was peeled off. Was not observed. In addition, the plating conductivity was cut off after 500 times of use, and the surface shape of the conductive DLC was observed with an electron microscope, but no change was observed in the shape.

(Measurement of volume resistivity)
In the same manner as in “(Conductive DLC film formation)”, an intermediate layer is formed on a glass plate and a conductive DLC film is formed thereon, and the volume resistivity is measured by a four-end needle resistance measurement method (Lorestar GP). , Manufactured by Mitsubishi Chemical Corporation). As a result, the volume resistivity was 2 × 10 ⁻³ Ω · cm.

(Formation of conductive DLC film)
The conductive DLC film was formed in the same manner as in Example 1, and a DLC layer was formed on a 100 mm square stainless steel substrate (hereinafter referred to as substrate).

(Formation of convex pattern)
A resist film (Photech RY3315, 10 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to the surface of the substrate on which the conductive DLC obtained above was formed. 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 in which a circular pattern that does not transmit light has a diameter of φ100 μm and a circular pattern pitch of 250 μm was placed on the surface of the substrate on which the conductive DLC was formed. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above the substrate on which the negative film was placed under a vacuum of 600 mmHg or less. further. By developing with a 1% aqueous sodium carbonate solution, a pattern made of a resist film (height 10 μm) having a circular pattern diameter of 98 to 101 μm and a circular pattern pitch of 250 μm was formed on the conductive DLC formation surface of the substrate.

(Formation of insulating layer)
The insulating layer was formed in the same manner as in Example 1.

(Concavity formation; removal of convex pattern with insulating layer attached)
By immersing the stainless steel substrate with the insulating layer attached in an aqueous solution of sodium hydroxide (10%, 50 ° C.), the resist film forming the convex pattern and the DLC film adhering thereto are peeled off, and the conductive substrate for plating is formed. Obtained.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 5 to 6 μm. The pitch of the circular pattern was 250 μm.

(Copper plating)
Using the conductive substrate for plating obtained above as a cathode, electrolytic copper plating was performed in the same manner as in Example 1, and plating was performed until the thickness of the metal deposited in the concave portion of the conductive substrate for plating was approximately 20 μm. . The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

(Peeling)
The copper plating part was peeled off as a copper foil from the copper-plated surface of the conductive substrate for plating. The line speed was 1 m / min. Then, a perforated copper foil having a pattern with a hole shape of φ57 to 63 μm and a hole pitch of 250 μm was obtained.

(Repeated use)
Next, as a result of repeating the copper plating-peeling step 100 times in the same manner as described above using the above conductive base material for plating, there was no change in the deposition and peelability of the copper plating, and the peeled portion of the insulating layer Was not observed. Moreover, the electroconductive for plating was cut off after 100 times of use, and the surface shape of the conductive DLC was observed with an electron microscope, but no change was observed in the shape.

(Formation of conductive DLC film)
The conductive DLC film was formed in the same manner as in Example 1, and a DLC layer was formed on a 100 mm square stainless steel substrate. Thereafter, the convex pattern and the insulating layer were not formed.

(Copper plating)
Using the conductive substrate for plating obtained above as a cathode, electrolytic copper plating was performed in the same manner as in Example 1, and plating was performed until the thickness of the deposited metal became approximately 20 μm.

(Peeling)
The copper plating part was peeled off as a copper foil from the copper-plated surface of the conductive substrate for plating. The line speed was 1 m / min. Then, a smooth copper foil was obtained.

(Repeated use)
Next, as a result of repeating the copper plating-peeling step 100 times in the same manner as described above using the above conductive base material for plating, there was no change in the deposition and peelability of the copper plating, and the peeled portion of the insulating layer Was not observed. Moreover, the electroconductive for plating was cut off after 100 times of use, and the surface shape of the conductive DLC was observed with an electron microscope, but no change was observed in the shape.

(Formation of conductive inorganic material film)
A chromium nitride film was formed using a coating apparatus (manufactured by HAUSER, HTC1500) having both a gas introduction pipe and a sputtering target in the apparatus. Specifically, a substrate (hereinafter referred to as “substrate”) in which hard chromium plating is applied to a thickness of 30 μm on 100 mm □ stainless steel (SUS304, mirror finish, thickness 0.5 mm, manufactured by Nisshin Steel Co., Ltd.) is placed in a vacuum chamber. After the substrate was cleaned by exciting plasma with Ar gas, chromium was sputtered to a thickness of 2 μm using chromium as a target and flowing nitrogen as a reactive gas, and chromium nitride was formed on the outermost surface. A substrate was obtained.

(Formation of convex pattern)
The convex pattern was formed in the same manner as in Example 1, and a convex pattern was formed on chromium nitride. Since this process was performed using the same mask under the same conditions, a lattice pattern made of a protrusion resist film (protrusion; height 10 μm) having a line width of 39 to 41 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was formed on the substrate. It was done.

(Formation of insulating layer)
The insulating layer was formed in the same manner as in Example 1.

(Concavity formation; removal of convex pattern with insulating layer attached)
The resist film forming the convex pattern and the DLC film attached thereto were peeled from the substrate to which the insulating layer was attached in the same manner as in Example 1 to obtain a conductive substrate for plating.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 5 to 6 μm. Moreover, the width | variety in the bottom part of a recessed part was 39-41 micrometers, and the width | variety (maximum width) in an opening part was 49-53 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
In the same manner as in Example 1, plating was performed until the thickness of the metal deposited in the recesses of the conductive base material for plating reached approximately 7 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

(Transcription)
The surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film for transfer prepared in Example 1 and the surface of the conductive substrate for plating that had been subjected to copper plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern of line width 63-69 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness (maximum) 7-8 micrometers was obtained. The shape of the conductor layer was wide from the lower part to the upper part (adhesive layer), reflecting the shape of the concave part, and the part overflowing from the concave part spread like an umbrella. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off.

(Repeated use)
Next, as a result of repeating the copper plating-peeling process 500 times in the same manner as described above using the conductive base material for plating, there is no change in the deposition property and the peelability of the copper plating, and the insulating layer is peeled off. Was not observed. Further, the plating conductivity was cut out and the surface shape of the chromium nitride was observed with an electron microscope, but no change was observed in the shape.

(Measurement of volume resistivity)
A conductive inorganic material film is formed on a glass plate in the same manner as described above in “(Formation of conductive inorganic material film)”, and volume resistivity is measured by a four-end needle resistance measurement method (Lorestar GP, Mitsubishi Chemical Corporation). Measured by the company). As a result, the volume resistivity was 7 × 10 ⁻⁴ Ω · cm.

(Formation of conductive DLC film)
A conductive DLC film was formed using a sputtering apparatus (UBMS504, manufactured by Kobe Steel, Ltd.). A 100 mm square titanium substrate (TP550, # 400 polished, thickness 0.5 mm, manufactured by Kobe Steel, Ltd., hereinafter referred to as “substrate”) is placed in a vacuum chamber, and the substrate is first cleaned by exciting Ar gas plasma. It was. An intermediate layer of 0.2 μm was formed using chromium as a target. First, tungsten carbide (WC) and carbon are simultaneously formed to form an inclined layer, and then only carbon is formed to form hydrogen-free conductive DLC until the thickness reaches 1 μm. A substrate formed on was obtained.

(Formation of convex pattern)
The convex pattern was formed in the same manner as in Example 1, and a convex pattern was formed on the conductive DLC. Since this process was performed using the same mask under the same conditions, a lattice pattern made of a protrusion resist film (protrusion; height 10 μm) having a line width of 39 to 41 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was formed on the substrate. It was done.

(Formation of insulating layer)
The insulating layer was formed in the same manner as in Example 1.

(Concavity formation; removal of convex pattern with insulating layer attached)
The resist film forming the convex pattern and the DLC film attached thereto were peeled from the substrate to which the insulating layer was attached in the same manner as in Example 1 to obtain a conductive substrate for plating.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 5 to 6 μm. Moreover, the width | variety in the bottom part of a recessed part was 39-41 micrometers, and the width | variety (maximum width) in an opening part was 49-53 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
In the same manner as in Example 1, plating was performed until the thickness of the metal deposited in the recesses of the conductive base material for plating reached approximately 7 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

(Transcription)
The surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film for transfer prepared in Example 1 and the surface of the conductive substrate for plating that had been subjected to copper plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern of line width 63-69 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness (maximum) 7-8 micrometers was obtained. The shape of the conductor layer was wide from the lower part to the upper part (adhesive layer), reflecting the shape of the concave part, and the part overflowing from the concave part spread like an umbrella. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off.

(Repeated use)
Next, as a result of repeating the copper plating-peeling step 300 times in the same manner as described above using the above conductive base material for plating, there was no change in the deposition and peelability of the copper plating, and the peeled portion of the insulating layer Was not observed. Moreover, the electroconductive for plating was cut off after 300 times of use, and the surface shape of the conductive DLC was observed with an electron microscope, but no change was observed in the shape.

(Measurement of volume resistivity)
In the same manner as in “(Conductive DLC film formation)”, an intermediate layer is formed on a glass plate and a hydrogen-free conductive DLC film is formed thereon, and the volume resistivity is measured by a four-end needle resistance measurement method. (Lorestar GP, manufactured by Mitsubishi Chemical Corporation). As a result, the volume resistivity was 3 × 10 ⁻⁴ Ω · cm. Further, without forming an intermediate layer on the glass plate, only a hydrogen-free conductive DLC film was formed in the same manner as described above, and the volume resistivity was measured in the same manner. As a result, the volume resistivity was 5Ω · cm.

The perspective view which shows an example of the electroconductive base material for plating of this invention. AA sectional drawing of FIG. Sectional drawing which shows an example of the process which shows the manufacturing method of the electroconductive base material for plating. Sectional drawing of the electroconductive base material for plating which has an intermediate | middle layer, and its precursor is shown. Sectional drawing which shows the first half of the example of preparation of the base material with a conductor layer pattern. Sectional drawing which shows the second half of the preparation examples of the base material with a conductor layer pattern. Sectional drawing which shows the state which formed the conductor layer pattern by plating in the recessed part of the electroconductive base material for plating. Sectional drawing of the base material with a conductor layer pattern obtained by transferring the conductor layer pattern in the recessed part shown in FIG. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using a rotary body. The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using the hoop-shaped electroconductive base material for plating. The bottom view which shows a part of perforated metal foil which is an example of patterned metal foil. FIG. 6 is a cross-sectional view taken along the line AA ′ in FIG. 5 (however, it is present on a conductive substrate for plating). Sectional drawing which shows another example of patterned metal foil (however, the state which exists on the electroconductive base material for plating).

Explanation of symbols

1: Conductive substrate for plating 2: Conductive substrate 3: Insulating layer 4: Recessed portion 5: Photosensitive resist layer (photosensitive resin layer)
6: Protrusion 7: DLC film 8: Intermediate layer 9: Conductor layer pattern 10: Transfer base material 11: Another base material 12: Adhesive layer 13: Other base material 14: Protective resin 15: Adhesive 16: Other substrate 17: Adhesive or adhesive 18: Protective film 19: Patterned metal foil 20: Hole 21: Stepped portion 22: Inclined portion 100: Electrolytic bath 101: Electrolytic solution 102: Anode 103: Rotating body 104: Piping 105: Pump 106: Metal 107: Film 108: Crimp roll 109: Substrate with conductor layer pattern 110: Hoop-like conductive substrate 111-128: Transport roll 129: Pretreatment tank 130: Plating tank (electrolytic bath)
131: Washing tank 132: Blackening treatment tank 133: Washing tank 134: Rust prevention tank 135: Washing tank 136: Plastic film substrate (adhesive film)
137: Crimp roll 138: Substrate with conductor layer pattern

Claims (40)

  A conductive base material for plating on which a conductive diamond-like carbon film or a conductive inorganic material film is formed.   A conductive substrate for plating comprising a substrate and a conductive diamond-like carbon film or a conductive inorganic material film formed on the surface of the substrate.   A conductive base material for plating including a base material and a conductive diamond-like carbon film formed on the surface of the base material, wherein the conductive diamond-like carbon film is a hydrogen-free diamond-like carbon film. Item 3. A conductive substrate for plating according to Item 2.   A conductive substrate for plating comprising a substrate and a conductive diamond-like carbon film formed on the surface of the substrate, wherein the conductive diamond-like carbon film contains impurities for imparting conductivity. The conductive substrate for plating according to claim 2, wherein the conductive substrate is for plating.   The conductive material for plating according to claim 2, which is a conductive substrate for plating including a substrate and a conductive inorganic material film formed on a surface of the substrate, wherein the conductive inorganic material film is a chromium nitride film. Base material.   An intermediate layer containing at least one of Ti, Cr, W, Si, Ta, Nb, Zr, or a nitride or carbide thereof is interposed between the base material and the conductive diamond-like carbon film or the conductive inorganic material film. The electroconductive substrate for plating according to any one of claims 2 to 5.   The conductive base material for plating according to any one of claims 2 to 6, wherein the surface of the base material is made of an alloy plating or sprayed metal of steel, Ti, nickel-base alloy, chromium or nickel.   A conductive base material on which a conductive diamond-like carbon film or a conductive inorganic material film is formed, and an insulating layer formed on the surface of the conductive diamond-like carbon film or the conductive inorganic material film; A conductive base material for plating, wherein the insulating layer has a recess that is wide in the opening direction and is formed to form a plating.   The conductive substrate for plating according to claim 8, wherein the conductive substrate includes a substrate and a conductive diamond-like carbon film or a conductive inorganic material film formed on the surface of the substrate.   10. The conductive base material includes a base material and a conductive diamond-like carbon film formed on a surface of the base material, and the conductive diamond-like carbon film is a hydrogen-free diamond-like carbon film. The electroconductive base material for plating as described.   10. The conductive base material includes a base material and a conductive diamond-like carbon film formed on the surface of the base material, and the conductive diamond-like carbon film contains impurities that impart conductivity. The electroconductive base material for plating as described.   The conductive base material for plating according to claim 9, wherein the conductive base material has a conductive inorganic material film made of a chromium nitride film formed on a surface thereof.   The conductive base material includes a base material and a conductive diamond-like carbon film formed on the surface of the base material, and Ti, Cr, W, Si, Ta are provided between the base material and the conductive diamond-like carbon film. The conductive substrate for plating according to claim 9, wherein an intermediate layer containing any one or more of Nb, Zr, nitrides or carbides thereof is interposed.   The conductive substrate for plating according to any one of claims 9 to 13, wherein the surface of the substrate is made of steel, Ti, nickel-base alloy, chromium or nickel alloy plating or sprayed metal.   The conductive substrate for plating according to any one of claims 8 to 14, wherein the recess for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself.   The conductive substrate for plating according to any one of claims 8 to 15, wherein the minimum width of the recesses is 1 to 40 µm, the maximum width of the recesses is 2 to 60 µm, and the interval between the recesses is 50 to 1000 µm.   The conductive substrate for plating according to any one of claims 8 to 16, wherein an angle of the side surface of the recess is 30 degrees or more and less than 90 degrees on the insulating layer side.   The conductive substrate for plating according to any one of claims 8 to 17, wherein the insulating layer is made of diamond-like carbon or an inorganic material.   The intermediate layer containing any one or more of Ti, Cr, W, Si, Zr, or a nitride or carbide thereof is interposed between the conductive substrate and the insulating layer. The electroconductive base material for plating as described. (A) A convex surface that can be removed on the surface of the conductive diamond-like carbon film or conductive inorganic material film of the conductive base material on which the conductive diamond-like carbon film or conductive inorganic material film is formed. Forming a pattern;
(B) The process of forming the insulating layer which consists of diamond-like carbon or an inorganic material on the surface of the electroconductive base material in which the convex-shaped pattern which can be removed is formed, and (C) The convex shape which the insulating layer has adhered The manufacturing method of the electroconductive base material for plating characterized by including the process of removing the pattern of this.   The method for producing a conductive substrate for plating according to claim 20, wherein the removable convex pattern is formed by a photolithography method using a photosensitive resist.   The pattern shape of the removable convex part has a width of 1 to 40 µm, an interval of 50 to 1000 µm, and a height of 1 to 30 µm, whereby a geometrical figure is drawn thereby. A method for producing a conductive substrate.   The method for producing a conductive substrate for plating according to any one of claims 20 to 22, wherein the insulating layer is diamond-like carbon or an inorganic material.   24. The production of a conductive substrate for plating according to any one of claims 20 to 23, wherein in the step of forming an insulating layer, an insulating film having different properties or characteristics is formed on the side surface of the convex pattern on the conductive substrate. Method.   25. The conductivity for plating according to claim 24, wherein in the step of forming the insulating layer, the hardness of the diamond-like carbon film that is the insulating layer to be formed is greater than the hardness of the diamond-like carbon film formed on the side surface of the convex pattern. A method for producing a substrate.   26. The plating according to claim 25, wherein the hardness of the diamond-like carbon film formed on the conductive substrate is 10 to 40 GPa, and the hardness of the diamond-like carbon film formed on the side surface of the convex pattern is 1 to 15 GPa. For producing a conductive base material for use.   In the step of forming the insulating layer, the boundary surface between the insulating layer formed on the conductive substrate and the insulating layer formed on the side surface of the removable convex pattern faces the outside of the convex pattern as a whole. The manufacturing method of the electroconductive base material for plating in any one of Claims 24-26 inclined.   The method for producing a conductive substrate for plating according to claim 27, wherein the angle of the boundary surface is formed to be 30 degrees or more and less than 90 degrees with respect to the surface of the conductive substrate.   29. The conductive film for plating according to any one of claims 20 to 28, wherein the diamond-like carbon film as an insulating layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization deposition method or a plasma CVD method. For producing a conductive substrate.   Before performing the step of forming the insulating layer on the surface of the conductive substrate on which the removable convex pattern is formed, on the surface of the conductive substrate on which the removable convex pattern is formed The method for producing a conductive substrate for plating according to any one of claims 20 to 29, wherein a step of forming an intermediate layer is performed.   The method for producing a conductive substrate for plating according to claim 30, wherein the intermediate layer contains one or more of Ti, Cr, W, Si, Ta, Nb, Zr, or a nitride or carbide thereof. (A) A step of depositing metal by plating in the concave portion of the conductive base material for plating according to any one of Items 8 to 19 and (B) a step of peeling the metal deposited in the concave portion of the conductive base material. A method for producing a conductor layer pattern, comprising: (B) a step of depositing a metal by plating in the concave portion of the conductive base material for plating according to any one of claims 8 to 19; and (b) another group of the metal deposited in the concave portion of the conductive base material. The manufacturing method of the base material with a conductor layer pattern characterized by including the process of transferring to a material.   The manufacturing method of the base material with a conductor layer pattern of Claim 33 which makes the thickness of the metal deposited by plating 2 times or less of the depth of a recessed part.   The method for producing a substrate with a conductor layer pattern according to any one of claims 33 and 34, wherein the another substrate has an adhesive layer having at least adhesiveness on the surface.   The manufacturing method of the base material with a conductor layer pattern in any one of Claims 33-35 including the process of blackening the metal deposited on the recessed part of the electroconductive base material for plating.   Furthermore, the manufacturing method of the base material with a conductor layer pattern in any one of Claims 33-36 including the process of blackening the metal pattern transcribe | transferred to another base material.   The base material with a conductor layer pattern manufactured by the method in any one of Claims 33-37.   A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to claim 38 with a resin.   A translucent electromagnetic wave shielding plate obtained by bonding the base material with a conductor layer pattern according to claim 38 or the translucent electromagnetic wave shielding member according to claim 39 to a transparent substrate.

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