JP5626419B2 - Conductive substrate for plating, manufacturing method thereof, manufacturing method of substrate with conductor layer pattern using the same, substrate with conductor layer pattern, translucent electromagnetic wave shielding member - Google Patents

Description

  The present invention relates to a conductive substrate for plating, a method for producing the same, a method for producing a substrate with a conductor layer pattern which is excellent in conductivity using the same, and is patterned to have light transmittance, and 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.

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

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 photoetching SiO ₂ on a conductive base material. However, 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. 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 a metal layer transfer base sheet. When transferring a transfer metal layer to an adhesive sheet, the electrical insulating layer on the electrodeposition substrate is subjected to peeling stress due to adhesive transfer, and there is a problem that the insulating layer peels off from the conductive substrate 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.

  In view of such problems, the present invention can produce a substrate with a conductor layer pattern patterned so as to have electrical conductivity and light transmittance with a high productivity by using a transfer method. An electroconductive substrate for plating which is easy to produce and a method for producing the same are provided. Moreover, this invention provides the manufacturing method of the base material with a conductor layer pattern using such an electroconductive base material, the base material with a conductor layer pattern, and an electromagnetic wave shielding member using the same.

The present invention relates to the following.
1. An electroconductive substrate for plating in which an insulating layer is formed on the surface of the electroconductive substrate, and a recess for forming a wide plating in the opening direction is formed in the insulating layer.
2. Item 2. The electroconductive substrate for plating according to item 1, 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.
3. Item 3. The conductive substrate for plating according to Item 1 or 2, wherein the insulating layer is made of diamond-like carbon (DLC) or an inorganic material.
4). Item 4. The conductive substrate for plating according to any one of Items 1 to ₃ , wherein the insulating layer is DLC, Al ₂ O ₃ or SiO ₂ .
5. Item 5. The conductive substrate for plating according to any one of Items 1 to 4, wherein the insulating layer is made of DLC having a hardness of 10 to 40 GPa.
6). Item 6. The conductive substrate for plating according to any one of Items 1 to 5, 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.
7). Item 7. The conductive substrate for plating according to any one of Items 1 to 6, wherein the side surface of the recess has an angle of 10 degrees or more and less than 90 degrees on the insulating layer side.
8). Item 8. The electroconductive substrate for plating according to any one of Items 1 to 7, wherein the side surface of the recess has an angle of 10 ° to 80 ° on the insulating layer side.
9. Item 9. The conductive substrate for plating according to any one of Items 1 to 8, wherein the insulating layer has a thickness of 0.5 to 20 µm.
10. Item 10. The plating according to any one of Items 1 to 9, wherein an intermediate layer containing at least one of Ti, Cr, W, Si, or a nitride or carbide thereof is interposed between the conductive substrate and the insulating layer. Conductive base material.
11. Item 11. The conductive substrate for plating according to any one of Items 1 to 10, wherein the surface of the conductive substrate is made of steel or Ti.
12 Item 12. The conductive substrate for plating according to any one of Items 1 to 11, which is wound around a conductive roll (drum) or a roll.
13. (A) forming a removable convex pattern on the surface of the conductive substrate;
(B) The process of forming the insulating layer which consists of DLC or an inorganic material on the surface of the electroconductive base material in which the convex pattern which can be removed is formed, and (C) The convex pattern which the insulating layer has adhered The manufacturing method of the electroconductive base material for plating characterized by including the process of removing.
14 Item 14. The method for producing a conductive substrate for plating according to Item 13, wherein the removable convex pattern is formed by a photolithography method using a photosensitive resist.
15. Item 15. The method for producing a conductive substrate for plating according to Item 13 or 14, wherein an insulating layer having different properties or characteristics is formed on the side surface of the convex pattern on the conductive substrate.
16. The distance from the side surface of the convex pattern (as a plane perpendicular to the base material) between the insulating layer formed on the conductive substrate and the insulating layer formed on the side surface of the convex pattern is the convex pattern. Item 16. The method for producing a conductive substrate for plating according to any one of Items 13 to 15, which is not reduced toward the standing position of the electrode but increases as a whole.
17. Item 17. The method for producing a conductive substrate for plating according to Item 16, wherein the angle of the boundary surface is formed to be 10 degrees or more and less than 90 degrees with respect to the conductive substrate.
18. Item 18. The method for producing a conductive substrate for plating according to Item 16 or 17, wherein the angle of the boundary surface is formed to be 10 degrees or more and 80 degrees or less with respect to the conductive substrate.
19. The conductive pattern for plating according to any one of Items 13 to 18, 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.
20. Item 20. The method for producing a conductive substrate for plating according to any one of Items 13 to 19, wherein the insulating layer is diamond-like carbon (DLC) or an inorganic material.
21. Item 21. The method for producing a conductive substrate for plating according to any one of Items 20 to 20, wherein the inorganic material is Al ₂ O ₃ or SiO ₂ .
22. Item 21. The method for producing a conductive substrate for plating according to Item 20, wherein the insulating layer is diamond-like carbon (DLC).
23. Item 23. The method for producing a conductive substrate for plating according to Item 22, wherein the hardness of the DLC film formed on the conductive substrate is larger than the hardness of the DLC film formed on the side surface of the convex pattern.
24. Item 24. The conductive substrate for plating according to Item 23, wherein the hardness of the DLC film formed on the conductive substrate is 10 to 40 GPa, and the hardness of the DLC film formed on the side surface of the convex pattern is 1 to 15 GPa. Manufacturing method.
25. Item 25. The method for producing a conductive substrate for plating according to any one of Items 22 to 24, wherein the DLC film 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.
26. 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 Items 13 to 25, wherein the step of forming an intermediate layer is performed.
27. Item 27. The method for producing a conductive substrate for plating according to Item 26, wherein the intermediate layer contains one or more of Ti, Cr, W, Si, nitrides or carbides thereof.
28. Item 28. The method for producing a conductive substrate for plating according to any one of Items 13 to 27, wherein the insulating layer has a thickness of 0.5 to 10 μm.
29. (A) a step of depositing a metal by plating on the concave portion of the conductive substrate for plating according to any one of Items 1 to 12,
(B) A process for producing a substrate with a conductor layer pattern, comprising a step of transferring the metal deposited in the concave portion of the conductive substrate to another substrate.
30. Item 30. The method for producing a substrate with a conductor layer pattern according to Item 29, wherein the thickness of the metal deposited by plating is not more than twice the depth of the recess.
31. Item 31. The method for producing a substrate with a conductor layer pattern according to Item 29 or 30, wherein the another substrate has an adhesive layer having at least adhesiveness on the surface.
32. Item 32. The method for producing a substrate with a conductor layer pattern according to Item 29 or 31, comprising a step of blackening the metal deposited in the concave portion of the conductive substrate for plating.
33. Furthermore, the manufacturing method of the base material with a conductor layer pattern in any one of claim | item 29-32 including the process of blackening the metal pattern transcribe | transferred to another base material.
34. Item 34. A substrate with a conductor layer pattern, produced by the method according to any one of Items 29 to 33.
35. Item 35. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 34 with a resin.
36. Item 35. A light transmitting electromagnetic wave shielding plate obtained by bonding the substrate with a conductor layer pattern according to Item 34 or the light transmitting electromagnetic wave shielding member according to Item 35 to a transparent substrate.

In the conductive base material for plating according to the present invention, since the concave portion where the metal layer is formed by plating is wide in the opening direction, the conductor layer pattern obtained by plating can be easily peeled off. Moreover, since an insulating layer consists of DLC or an inorganic material, the adhesiveness to an electroconductive base material is excellent, 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.
The conductive substrate for plating having a wide concave portion toward the opening direction of the present invention is a convex shape in which a convex pattern is formed on the conductive substrate and the insulating layer is adhered after the insulating layer is formed. Since the concave portion can be produced by removing the pattern, the manufacture is easy and the productivity is high.

  According to the method for producing a conductive substrate for plating of the present invention, the number of steps is small, and in particular, a wide concave portion can be easily produced in the opening direction, so that it can be produced 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 is easily peeled off, a substrate with a conductor layer pattern having excellent light transmittance can be easily produced. In addition, it is possible to easily produce a substrate with a conductor layer pattern that is excellent in electromagnetic shielding properties or conductivity. 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 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 electroconductive substrate for plating in the invention is 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 widened in the opening direction. A concave portion (plating portion) for forming an appropriate plating is formed. The conductive material is exposed on the bottom surface of the recess.

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

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

  The thickness of the insulating layer corresponds to the depth of the recess. Since the depth of the recess is related to the thickness of the plating to be deposited, it is appropriately determined according to the purpose. The thickness of the insulating layer is preferably in the range of 0.10 μm to 100 μm, and more preferably in the range of 0.5 μm to 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 academic figures, and these may be combined as appropriate. 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, the insulating layer 3 is laminated on the conductive base material 2, the concave portion 4 is formed in the insulating layer 3, and the conductive base material 2 is formed at the bottom of the concave portion 4. 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 off 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 and the opposite surface thereof be perpendicular to the bottom surface so that no portion 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１０度以上９０度未満が好ましく、１０度以上８０度以下がより好ましく、３０度以上６０度以下が特に好ましい。この角度が小さいと作製が困難となる傾向があり、３０度以上がより好ましく、大きいと凹部にめっきにより形成し得た金属層（導体層パターン）を剥離する際、又は、別の基材に転写する際の抵抗が大きくなる傾向があり、８０度以下がより好ましい。 The side surface of the recess is not necessarily a flat surface. In this case, as shown in FIG. 2 (b), the gradient α is such that the height h of the recess (this is the thickness of the insulating layer) and the width s of the side surface of the recess (in the horizontal direction). The width direction of the side surface of the recess)

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

The planar shape of the insulating layer and the thickness of the insulating layer or the depth of the recess in the conductive substrate for plating of the present invention are appropriately determined according to the use of the patterned metal obtained using the conductive substrate for plating of the present invention. Is done.
The concave portion of the conductive base material for plating corresponds to the shape of the patterned metal generated by plating, 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 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. Further, the insulating layer 3 preferably has a bottom area of 1 × 10 ² to 1 × 10 ⁴ square microns, and more preferably has an insulating layer interval of 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 according to the present invention includes a step of forming an insulating layer on the surface of the conductive substrate so that a geometric figure is drawn by the recesses exposing the conductive substrate. .
This step includes (A) a step of forming a removable convex pattern on the surface of the conductive substrate,
(B) including a step of forming an insulating layer on the surface of the conductive substrate on which a removable convex pattern is formed, and (C) a step of removing the convex pattern to which the insulating layer is attached. .

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 in contact with 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, a sectional shape of the projection portion 6, as a method for the maximum value d ₁ of the width of the projecting portion 6 is larger or equal to the width d ₀ in contact with the projecting portion 6 and the conductive substrate 2, the developing of the protrusion 6 A resist having a characteristic that sometimes over-develops or has an undercut shape may be used. It is preferable that d ₁ is realized at the upper part of the 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 composed 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 the plasma CVD method, a hydrocarbon-based gas is preferably used as a carbon source as a raw material. For example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butene, pentene, alkadiene gases such as pentadiene, butadiene, acetylene, methylacetylene, etc. Alkyne gases, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cycloalkene gases such as cyclopentene and cyclohexene, methanol And alcohol gases such as ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as methanal and ethanal. The said gas may be used independently and may use 2 or more types together. Further, a mixture of the above-described carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and the above-described carbon source and a gas of a compound composed only of carbon and oxygen such as carbon monoxide gas and carbon dioxide gas. A mixture of a compound gas composed of only carbon and oxygen, such as a mixture, carbon monoxide gas, carbon dioxide gas, and hydrogen gas; a compound gas composed of only carbon and oxygen, such as carbon monoxide gas, carbon dioxide gas; Examples thereof include a mixture with oxygen gas or water vapor. Further, these source gases may contain a rare gas. The rare gas is a gas composed of an element belonging to Group 0 of the periodic table, and examples thereof include helium, argon, neon, and xenon. These rare gases may be used alone or in combination of two or more.

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

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

Next, the step (C) of removing the convex pattern to which the insulating layer is attached will be described. 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.
The distance from the side surface of the convex pattern (as a plane perpendicular to the base material) between the insulating layer formed on the conductive substrate and the insulating layer formed on the side surface of the convex pattern is the convex pattern. It is preferable that it does not become small toward the standing position, but becomes large as a whole.
The side surface of the convex pattern (as a surface perpendicular to the conductive substrate) is the surface if the side surface of the convex pattern is perpendicular to the substrate, but the side surface of the convex pattern is the base. In the case of covering the material side, the side surface of the convex pattern is a vertical surface raised vertically from a point ending with the conductive base material.
When the protrusion 6 is removed, the insulating layer is separated at this boundary, and as a result, the side surface of the recess has an inclination angle α. The inclination angle α is preferably 10 degrees or more and less than 90 degrees, more preferably 10 degrees or more and 80 degrees or less, further preferably 30 degrees or more and 60 degrees or less, particularly preferably 40 degrees or more and 60 degrees or less, and the DLC film is plasma-treated. In the case of manufacturing by CVD, it becomes easy to control at about 40-60 degrees. That is, the concave portion 4 is formed so as to become wider toward the opening direction. As a method of controlling the inclination angle α, a method of adjusting the height of the protrusion 6 is preferable. As the height of the protrusion 6 increases, the inclination angle α can be controlled more greatly.

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

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. 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) 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 the present invention, the substrate with a conductor layer pattern is
(B) by a method including a step of depositing a metal by plating in the concave portion of the conductive base material for plating, and (b) a step of transferring the metal deposited in the concave portion of the conductive base material to another base material. Manufactured.

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

Next, the electroless plating will be further described. Typical examples of the electroless plating method include copper plating, 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 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, one that forms a stable soluble complex with nickel ions in the plating solution is used, and acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycine, alanine, EDTA, etc. are used. In this case, sulfur compounds and lead ions are added. 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 or their alloys, and stainless steel In this case, in order to impart catalyst activation, a method is used in which the object to be plated is immersed in an acidic hydrochloric acid solution of palladium chloride and palladium is deposited on the surface by ion substitution.

The electroless plating that can be used in the present invention is, for example, immersed in an electroless copper plating solution at a temperature of about 60 to 90 ° C. after a palladium catalyst is 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 μΩ · cm), iron (9.0 μΩ · cm), chromium (17 μΩ · cm, all values at 20 ° 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 in the concave 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 polyethersulfone. A film made of plastic such as phon, polycarbonate, polyamide, polyimide, acrylic resin, etc., having a total visible light transmittance of 70% or more is preferable. These can be used as a single layer, but may be used as a multilayer film in which two or more layers are combined. Among the plastic films, a polyethylene terephthalate film or a polycarbonate film is particularly preferable from the viewpoints of transparency, heat resistance, ease of handling, and cost.
Although there is no restriction | limiting in particular in the thickness of the said plastic film, The thing of 1 mm or less is preferable, and when it is too thick, there exists a tendency for visible light transmittance | permeability to fall easily. 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, 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 conductor layer pattern of the finally obtained base material with a conductor layer pattern (meaning the conductor layer pattern that has been 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. When the conductor layer pattern obtained by the present invention is used on the front surface of the display, the aperture ratio needs to be 50% or more, more preferably 60% or more. If the line interval becomes too large, the electromagnetic wave shielding property is deteriorated. Therefore, the line interval is preferably set to 1000 μm (1 mm) or less. When the line interval is complicated by a combination of geometric figures or the like, the area is converted into a square area with the repetition unit as a reference, and the length of one side is set as the line interval.

  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.

The thickness of the metal foil formed by plating is reduced from the viewpoint that the metal layer to be deposited can be more shaped by making the recess deeper relative to the thickness of the deposited metal layer. The height of the insulating layer is preferably 2 times or less, particularly preferably 1.5 times or less, and further preferably 1.2 times or less, but is not limited thereto.
The degree of plating can be such that the deposited metal layer is present in the recess. Even in such a case, since the concave shape is wide in the opening direction, and 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 recesses 4 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 substrate 10 is peeled off, the conductor layer pattern 9 is adhered to the pressure-sensitive adhesive layer 12 and peeled from the recess 4 of the conductive substrate 1 for plating. As a result, the substrate 13 with a conductor layer pattern is formed. Is obtained (FIG. 6 (h)).

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 is formed in the recess 4 of the conductive substrate 1 for plating. There is a method of blackening the conductive layer pattern 9 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. Can be obtained.
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 may be a material with relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. preferable. By using a rotating body as the conductive base material, it is possible to obtain a base material with a conductor layer pattern as a roll, and in this case, productivity is greatly increased.

  A process of obtaining a structure as a scroll while continuously peeling a pattern formed by 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 conductive substrate is made of a material having relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. It is preferable. When a hoop-like conductive substrate is used, the blackening treatment, rust prevention treatment, transfer and other processes can be performed in one continuous process, so the productivity of the substrate 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 a conductor layer pattern required for an electromagnetic wave shielding member is produced, if the region is defined as region A, the conductive base material for plating according to the present invention includes a region (region) 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.
Further, the formation of the recesses in the region B, the formation of the insulating layer, and the like can be performed in the same manner as in the region A described above. Furthermore, it is preferable that the depth of the recess and the recess be 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 in the portion that bears the electromagnetic wave shielding function is preferably 10 μm or less, and 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 an optical film member.

In the manufacturing method of the base material with the conductor layer pattern described above,
Another substrate used for transfer is used as an adhesive film for peeling, and is used to peel the metal deposited in the recesses of the conductive substrate, and the transferred conductor layer pattern is used as another substrate. Further, it may be used after being peeled off.

Moreover, in the manufacturing method of the base material with a conductor layer pattern demonstrated above,
(B) Instead of transferring the metal deposited in the recesses of the conductive substrate to another substrate, (b ') without using the adhesive film for the metals deposited in the recesses of the conductive substrate A patterned metal foil can be produced by making the process of peeling itself.

Example 1
(Formation of convex pattern)
A resist film (Photech RY3315, 10 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 150 mm square stainless steel plate (SUS316L, mirror polished, thickness 300 μm, manufactured by Nisshin Steel Co., Ltd.) (FIG. 3). Corresponding to (a)). The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the line width of the light transmission part is 15 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square). Then, the negative film in which the pattern was formed in a grid shape with a size of 120 m square was left on one side of the stainless steel plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the stainless plate on which the negative film was placed under a vacuum of 600 mmHg or less. Furthermore, by developing with a 1% aqueous sodium carbonate solution, a lattice pattern comprising a protrusion resist film (protrusion; height 10 μm) having a line width of 16 to 19 μm, a line pitch of 300 μm, and a bias angle of 45 degrees on a SUS plate Formed. Note that the entire surface opposite to the surface on which the pattern is formed is exposed and is not developed, and a resist film is formed on the entire surface (corresponding to FIG. 3B). The line width is the maximum width (d ₁ ) of the protrusion, and is the width at the top of the protrusion. The width (d ₀ ) of the contact portion of the protrusion with the conductive substrate was 0 to about 0.8 μm smaller than this maximum width. Further, the minimum width of the protrusion is 0 to about 1.5 μm smaller than the maximum width (d ₁ ), and is the width of the portion slightly higher than the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.

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

(Concavity formation; removal of convex pattern with insulating layer attached)
The stainless steel substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating (corresponding to FIG. 3D).
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 5 to 6 μm. Moreover, the width | variety in the bottom part of a recessed part was 16-19 micrometers, and the width | variety (maximum width) in an opening part was 26-31 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 250 g / L, sulfuric acid 70 g / L, sulfuric acid 70 g / L, cube) using the electroconductive substrate for plating with the adhesive film attached as a cathode and phosphorus-containing copper as an anode Immerse it in 4 ml / L aqueous solution (30 ° C.) of light AR (supplied by Sakakibara Eugelite Co., Ltd.), apply voltage to both electrodes to make the current density 10 A / dm ² , 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)
A primer (HP-1; manufactured by Hitachi Chemical Co., Ltd.) is 1 μm thick on the surface of a 100 μm thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) 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 20-25micrometer, line pitch 300 +/- 2micrometer, and conductor layer thickness (maximum) 7-8 micrometers was obtained. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.
As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off. The line width and conductor layer thickness were measured by partially cutting out the obtained base material with a conductor layer pattern and casting it with a resin, and observing the cross section with a magnification of 3000 times by SEM. Since the measurement points were 5 and both sides of the recess were measured, the maximum and minimum values of 10 points in total were adopted (the same applies below). The line pitch was measured using a microscope (digital microscope VHX-500, manufactured by Keyence Corporation) at a magnification of 200 times, and the measurement was performed at five random points (the same applies to the following). ).

(Formation of protective film)
The surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV curable resin HITAROID 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film (macro hole DE, Bayer Co., Ltd.). And the conductor layer pattern is embedded in the UV curable resin and 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 transferability of the copper plating, and the peeling portion of the insulating layer was also observed. There wasn't.

Example 2
(Formation of convex pattern)
A liquid resist (ZPN-2000, manufactured by Nippon Zeon Co., Ltd.) was applied on both sides to a 150 mm square titanium plate (pure titanium, mirror polished, thickness 400 μm, manufactured by Nippon Metal Co., Ltd.). By applying three times, a resist film having a thickness of 6 μm was obtained. After pre-baking at 110 ° C. for 1 minute, the line width of the light transmission part is 5 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line has an angle of 45 degrees with respect to the side of the regular square. Thus, a negative chrome mask in which a lattice-like pattern was formed with a size of 110 mm square was allowed to stand on one side of a titanium plate. Using an ultraviolet irradiation device, the substrate was adsorbed under a vacuum of 600 mmHg or less, and ultraviolet rays were irradiated at 200 mJ / cm ² from the titanium plate on which the chromium mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 115 ° C. for 1 minute and developing with 2.38% tetramethylammonium hydroxide (TMAH), the resist film has a line width of 5 to 7 μm, a line pitch of 300 μm, and a bias angle of 45 ° on a titanium plate. A lattice pattern consisting of was formed. The line width is the maximum width (d ₁ ) of the protrusion, and is the width at the top of the protrusion. The width (d ₀ ) of the contact portion between the protrusion and the conductive substrate was 0 to about 0.5 μm smaller than this maximum width. Further, the minimum width of the protrusion is 0 to about 1 μm smaller than the maximum width (d ₁ ), and is a width at a slightly higher position from the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.

(Formation of insulating layer)
After coating to the intermediate layer as in Example 1, DLC was coated to a thickness of 2 to 2.5 μm. At this time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 1.8 to 2.5 μm. The angle of the boundary surface was 45 to 48 degrees. The film thickness and the interface angle were measured in the same manner as in Example 1.
(Concavity formation; removal of convex pattern with insulating layer attached)
The titanium substrate on which the insulating layer was adhered was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 2 hours while applying ultrasonic waves at 50 kHz. 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 2 to 2.5 μm. Further, the width (maximum width) at the opening portion was 9 to 12 μm with respect to the width 5 to 7 μm at the bottom of the concave portion. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. An electrolysis bath for electrolytic copper plating using the conductive substrate for plating with the adhesive film attached as a cathode and a copper plate as an anode (copper pyrophosphate: 100 g / L, potassium pyrophosphate: 250 g / L, aqueous ammonia ( 30%): 2 mL / L, pH: 8-9, bath temperature: 30 ° C.), a voltage is applied to both electrodes to set the cathode current density to 5 A / dm ² , and deposits in the recesses of the conductive substrate for plating. The plating was performed until the thickness of the finished metal was approximately 3.5 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

(Transcription)
The copper pattern formed on the electroconductive substrate for plating was transferred to the adhesive film in the same manner as in Example 1. The base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern of line width 11-14 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness 3-4 micrometers was obtained. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.
As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off.
Further, a protective film was formed in the same manner as in Example 1 to obtain a substrate with a conductor layer pattern having a protective film.

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

Example 3
A liquid resist (KMPR-1050, manufactured by Nippon Kayaku Co., Ltd.) was applied to both surfaces of a stainless steel substrate (SUS304, 314 × 150 mm, manufactured by Nisshin Steel Co., Ltd.) with a thickness of 15 μm. After prebaking at 90 ° C. for 10 minutes, the line width of the light transmission part is 5 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is at an angle of 45 degrees with respect to the side of the regular square. Thus, two negative chrome masks in which a lattice-like pattern was formed with a size of 110 mm □ were placed side by side on one side of a stainless steel plate and allowed to stand. The substrate was adsorbed under a vacuum of 600 mmHg or less using an ultraviolet irradiation device, and ultraviolet rays were irradiated at 200 mJ / cm ² from the stainless steel plate on which the chromium mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 95 ° C. for 7 minutes and developing with 2.38% tetramethylammonium hydroxide (TMAH), a resist film having a line width of 5 to 7 μm, a line pitch of 300 μm, and a bias angle of 45 ° on a stainless steel plate A pattern consisting of The line width is the maximum width (d ₁ ) of the protrusion, and is the width at the top of the protrusion. The width (d ₀ ) of the contact portion of the protrusion with the conductive substrate was 0 to about 1 μm smaller than the maximum width. In addition, the minimum width of the protrusion is 0 to about 2 μm smaller than the maximum width (d ₁ ), and is the width of the portion slightly higher than the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.

(Formation of insulating layer)
As in Example 2, DLC was coated to a thickness of 3 to 4 μm. At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 3 to 4 μm. The angle of the boundary surface was 45 to 47 degrees.

(Concavity formation; removal of convex pattern with insulating layer attached)
The stainless steel substrate on which the insulating layer was adhered was immersed in a resist stripping solution (RemoverPG, Nippon Kayaku Co., Ltd., 70 ° C.) and left for 8 hours with occasional rocking. The resist film 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 3 to 4 μm. Moreover, the width | variety in the bottom part of a recessed part was 5-7 micrometers, and the width | variety (maximum width) in an opening part was 11-15 micrometers. The pitch of the recesses was 300 μm.

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

(Transcription)
The pressure-sensitive adhesive film produced in Example 1 was once wound up in a roll shape to obtain a roll-shaped pressure-sensitive adhesive film. The pressure-sensitive adhesive film 107 is unwound from the roll-shaped pressure-sensitive adhesive film, and the surface of the pressure-sensitive adhesive layer is applied to the metal (copper) 106 deposited on the rotating body (stainless steel roll) by the pressure roll 108 under the same laminating conditions as in Example 1. The metal 106 was transferred to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film by continuously bonding and peeling, and the substrate 109 with a conductor layer pattern was continuously prepared. The base material 109 with the conductor layer pattern was wound into a roll (not shown). Moreover, blocking at the time of winding was prevented by laminating release PET (S-32, manufactured by Teijin DuPont Co., Ltd.) while laminating on the surface of the adhesive film on which the conductor layer pattern was transferred. The conductor layer pattern had a line width of 14 to 18 μm, a line pitch of 300 ± 2 μm, and a conductor layer thickness of 4.5 to 6.5 μm. Even after 50 m of the adhesive film to which the copper plating had been transferred was wound up, there was no change in the copper plating on the stainless steel roll and its transferability, and no peeling of the insulating layer was observed. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.

(Formation of protective film)
A portion of the obtained base material with a conductor layer pattern is cut off, and a UV curable resin (Aronix UV-3701, manufactured by Toagosei Co., Ltd.) is applied to the surface on which the conductor layer pattern is formed. After coating the PET film (Mylar D, made by Teijin DuPont Films Co., Ltd., 75 μm) gently using a hand roll so that air bubbles do not enter, Then, a protective film was formed by irradiating with 1 J / cm ² of ultraviolet rays.

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

Example 4
(Formation of convex pattern)-(Removal of convex pattern with insulating layer attached)
A convex pattern was formed in the same manner as in Example 1, an insulating layer was formed in a thickness of 5 to 6 μm, the convex pattern to which the insulating layer was attached was removed, and a conductive substrate for plating was produced.

(Copper plating)
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive base material for plating obtained above was not formed. Electrolytic baths for electrolytic copper plating (copper sulfate (pentahydrate) 255 g / L, sulfuric acid 55 g / L, sulfuric acid 55 g / L, cube) using the conductive substrate for plating with the adhesive film attached as a cathode and phosphorus-containing copper as an anode Immerse it in a light # 1A (Sugihara Eugelite Co., Ltd. additive, 4 ml / L aqueous solution, 20 ° C.) and apply voltage to both electrodes to make the cathode current density 7 A / dm ² . Plating was performed until the thickness of the metal deposited in the recess became approximately 4 μm. Copper plating did not reach the line opening, and the plated state was as shown in FIG.

(Transcription)
The surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film for transfer produced 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 plate for plating transfer was peeled off, the copper deposited in the concave portions of 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 22-27 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness 3-4 micrometers was obtained. The shape of the conductor layer, reflecting the shape of the recess, was wider from the lower part toward the upper part (adhesive layer) as shown in FIG.

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

(Comparative Example 1)
(Formation of convex pattern)
A convex pattern was formed in the same manner as in Example 1 to obtain a convex pattern having a thickness of 10 μm, a line width of 16 to 19 μm, and a line pitch of 300 μm. At that time, one end of the surface of the conductive substrate was left unexposed so that the base metal was exposed after development.

(Formation of insulating layer)
Next, the conductive substrate on which the convex pattern is formed is used as a cathode, the portion where the above-mentioned base metal is exposed is connected to the electrode with a clip, the anode is a stainless steel (SUS304) plate, and the cationic electrodeposition paint ( Insulated 3020, manufactured by Nippon Paint Co., Ltd.), the conductive substrate was electrodeposited under the condition of 15 V for 10 seconds. After washing with water and drying at 110 ° C. for 10 minutes, an insulating layer was formed by baking under a nitrogen stream at 230 ° C. for 40 minutes. The oxygen concentration in the furnace was 0.1%. The thickness of the insulating layer formed on the flat portion was approximately 2.5 μm. Since the electrodeposition paint is not deposited on the part that is not energized, it is not deposited around the convex part, but the electrodeposition paint adhering to the resist film could not be cleaned, so both sides of the convex part formed by the resist film were not cleaned. Also, an electrodeposition coating film was adhered, and the thickness thereof was 0.2 to 0.7 μm. In the case of the electrodeposition paint, the boundary surface between the convex pattern side portion and the film formed on the flat portion was not formed.

(Removal of convex pattern with insulating layer attached)
The stainless steel substrate coated with the electrodeposition paint was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 15 minutes with occasional shaking. The resist film forming the convex pattern and the electrodeposition paint adhering thereto have been peeled off. The side part of the line had various shapes, but there were many places where the wide concave part was not formed in the opening direction, and the boundary surface of the insulating layer was not smooth, but there were many places with broken surfaces. It was. In addition, the line was also slightly wobbled.

(Copper plating)
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the uneven pattern of the conductive substrate for plating obtained above was not formed. Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 70 g / L, sulfuric acid 180 g / L, sulfuric acid 180 g / L, capalaside) using the conductive substrate for plating with the adhesive film attached as a cathode and phosphorous copper as an anode HL (manufactured by Atotech Japan Co., Ltd., additive), 20 ° C.), a voltage is applied to both electrodes, and the current density is 8 A / dm ^2. Plating was performed until the thickness was approximately 5 μm.

(Transcription)
The copper pattern formed on the electroconductive substrate for plating was transferred to the adhesive film in the same manner as in Example 1. The base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern of line width 20-33 micrometers, line pitch 300 +/- 2micrometer, and the thickness of a conductor layer 4.7-6 micrometers was obtained. The line after transfer reflected the shakiness of the line of the conductive substrate, and the shakiness was seen. 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.
Further, a protective film was formed in the same manner as in Example 1 to obtain a substrate with a conductor layer pattern having a protective film.

(Repeated use)
Then, using the conductive substrate for plating, the copper plating-transfer process was repeated in the same manner as described above. As a result, the transferability of copper plating gradually deteriorated, and the peeled portion of the insulating layer was visually recognized at the fifth time. did it.

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

1: Conductive substrate for plating 2: Conductive substrate 3: Insulating layer 4: Recessed portion 5: Photosensitive resist layer (photosensitive resin layer)
6: Projection 7: DLC film 8: Intermediate layer 9: Conductive 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 pressure sensitive adhesive 18: protective film 100: electrolytic bath 101: electrolytic solution 102: anode 103: rotating body 104: pipe 105: pump 106: metal 107: film 108: pressure roll 109: conductor layer Patterned base material 110: Hoop-like conductive base materials 111 to 128: Conveying roll 129: Pretreatment tank 130: Plating tank (electrolytic bath)
131: Water washing tank 132: Blackening treatment tank 133: Water washing tank 134: Rust prevention treatment tank 135: Water washing tank 136: Plastic film substrate (adhesive film)
137: Press roll 138: Substrate with conductor layer pattern

Claims (34)

(A) forming a removable convex pattern on the surface of the conductive substrate;
(B) A step of forming an insulating layer made of diamond-like carbon ( DLC ) or an inorganic material on the surface of the conductive substrate on which the removable convex pattern is formed; and (C) the insulating layer is attached. a step of removing the convex patterns are seen including,
In the step (B), an insulating film having a different property or characteristic is formed on the side surface of the convex pattern on the conductive substrate, so that the insulating layer of the insulating film formed on the conductive substrate A boundary surface is formed between the insulating layer and the insulating layer formed on the side surface of the pattern, and the distance from the side surface of the convex pattern (as a surface perpendicular to the substrate) of the boundary surface is the convex pattern A method for producing a conductive substrate for plating, characterized by forming an insulating layer that is not reduced in size toward the standing position but increased as a whole .   The method for producing a conductive substrate for plating according to claim 1, wherein the removable convex pattern is formed by a photolithographic method using a photosensitive resist. The method for producing a conductive substrate for plating according to claim 1 or 2 , wherein the angle of the boundary surface is formed to be 10 degrees or more and less than 90 degrees with respect to the conductive substrate. The method for producing a conductive substrate for plating according to any one of claims 1 to 3, wherein the angle of the boundary surface is formed to be 10 degrees or more and 80 degrees or less with respect to the conductive substrate. Pattern of removable projections, the width 1 to 40 [mu] m, distance a is 50~1000μm and height 1 to 30 [mu] m, to one of the claims 1-4 whereby those whose geometry is drawn The manufacturing method of the electroconductive base material for plating of description. The method for producing a conductive substrate for plating according to any one of claims 1 to 5 , wherein the insulating layer is an inorganic material . The method for producing a conductive substrate for plating according to claim 6, wherein the inorganic material is any one of Al ₂ O ₃ and SiO ₂ . The method for producing a conductive substrate for plating according to any one of claims 1 to 5 , wherein the insulating layer is diamond-like carbon (DLC). The method for producing a conductive substrate for plating according to claim 8, wherein the hardness of the DLC film formed on the conductive substrate is larger than the hardness of the DLC film formed on the side surface of the convex pattern. The conductive group for plating according to claim 9 , wherein the hardness of the DLC film formed on the conductive substrate is 10 to 40 GPa, and the hardness of the DLC film formed on the side surface of the convex pattern is 1 to 15 GPa. A method of manufacturing the material. The method for producing a conductive substrate for plating according to any one of claims 8 to 10 , wherein the DLC film 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. . 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 1 to 11 , wherein a step of forming an intermediate layer is performed. The manufacturing method of the electroconductive base material for plating of Claim 12 in which an intermediate | middle layer contains any one or more of Ti, Cr, W, Si, those nitrides, or carbides. The thickness of the insulating layer, production method for plating conductive substrate according to any one of claims 1 to 13, which is a 0.5 to 10 [mu] m. (A) By the method for producing a conductive substrate for plating according to any one of claims 1 to 14, a step of obtaining a conductive substrate for plating, and plating in the recesses of the obtained conductive substrate for plating Depositing metal,
(B) A process for producing a substrate with a conductor layer pattern, comprising a step of transferring the metal deposited in the concave portion of the conductive substrate to another substrate. The manufacturing method of the base material with a conductor layer pattern of Claim 15 which makes 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 claim 15 or 16 , 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 15-17 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 15-18 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 15-19 . The translucent electromagnetic wave shielding member formed by coat | covering the conductor layer pattern of the base material with a conductor layer pattern of Claim 20 with resin. A translucent electromagnetic wave shielding plate obtained by bonding the base material with a conductor layer pattern according to claim 20 or the translucent electromagnetic wave shielding member according to claim 21 to a transparent substrate. Either obtained by the production method of plating a conductive substrate according to claim 1-14,
An insulating layer is formed on the surface of the conductive base material, and a concave portion for forming a wide plating in the opening direction is formed in the insulating layer, and the side surface of the concave portion is the boundary surface . Conductive substrate. The conductive substrate for plating according to claim 23 , wherein the concave portion for forming the plating is formed so as to draw a geometric figure on the insulating layer or to draw a geometric figure itself. The conductive substrate for plating according to claim 23 or 24 , wherein the insulating layer is made of diamond-like carbon (DLC) or an inorganic material. Insulating layer, DLC, _Al 2 _{O 3} or plating a conductive substrate according to any one of SiO ₂ and is claim 23-25. The conductive substrate for plating according to any one of claims 23 to 26 , wherein the insulating layer comprises a DLC film having a hardness of 10 to 40 GPa. Minimum width of the recess is 1 to 40 [mu] m, for plating the conductive substrate according to any one of claims 23 to 27 the maximum width of the recess spacing of 2~60μm and recesses is 50 to 1000 [mu] m. The conductive substrate for plating according to any one of claims 23 to 28 , wherein an angle of the side surface of the recess is 10 degrees or more and less than 90 degrees on the insulating layer side. The conductive substrate for plating according to any one of claims 23 to 29 , wherein the angle of the side surface of the recess is 10 degrees or more and 80 degrees or less on the insulating layer side. The conductive substrate for plating according to any one of claims 23 to 30, wherein the insulating layer has a thickness of 0.5 to 10 µm. Between the conductive substrate and the insulating layer, Ti, Cr, W, according to any one of claims 23 to 31 which is interposed Si or intermediate layer containing any one or more of these nitride or carbide Conductive substrate for plating. The conductive substrate for plating according to any one of claims 23 to 32 , wherein the surface of the conductive substrate is made of steel or Ti. The conductive substrate for plating according to any one of claims 23 to 33 , wherein the substrate is wound around a conductive roll (drum) or a roll.

Images