JP2009152285A - Method for manufacturing metal pattern and base material having conductive layer pattern, and base material having conductive layer pattern and electromagnetic wave shielding member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a metal pattern subjected to more homogeneous blackening treatment and a base material having a conductive layer pattern in the tone of color and shape having a sufficient degree of blackening for metal having a geometrical figure, and to provide the base material having a conductive layer pattern and an electromagnetic wave shielding member using the base material having a conductive layer pattern. <P>SOLUTION: In the method for manufacturing the metal pattern 9 where a surface subjected to blackening treatment by depositing metal in a conductive metal pattern in a geometrical figure shape by pulse electrolysis is subjected to blackening treatment, a pulse electrolysis is performed under conditions for maintaining a cycle rate to be ≥2% or ≤90% and for holding each pulse conduction time to be ≥2 ms and ≤200 ms, when high conduction time is set to T<SB>1</SB>, low conduction time is set to T<SB>2</SB>, one cycle is defined to be the sum of T<SB>1</SB>and T<SB>2</SB>, and the cycle rate E in pulse electrolysis is set to E=100×(T<SB>1</SB>/(T<SB>1</SB>+T<SB>2</SB>)). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a metal pattern patterned to have excellent electrical conductivity and light transmission, a method for producing a substrate with a conductor layer pattern having the metal pattern, a substrate with a conductor layer pattern, and electromagnetic wave shielding using the same It relates to members.

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

  Among these, when shielding the electromagnetic wave on the transparent glass surface, the transparent resin panel surface, the display surface of a display such as a cathode ray tube (CRT) or a plasma display panel (PDP), the electromagnetic shielding member is required to be as thin as possible. In addition, an electromagnetic wave shielding member having a metal mesh as an electromagnetic wave shielding layer has become mainstream as a light balance (transparency) and an electromagnetic wave shielding property opposite to this in a balanced manner. .

  In order to enhance the brightness of the transmitted light from the display (hereinafter referred to as visibility), it is desirable that at least the viewer side of the metal mesh is black, so that the metal mesh is black to improve the visibility. It is done to process.

  In Patent Document 1, a metal pattern is produced by electrodepositing a metal using a metal electrolyte on an electrodeposition substrate capable of metal electrodeposition in a mesh form, and thereafter, an electromagnetic wave shielding substrate via an adhesive. Describes a method for producing an electromagnetic wave shielding plate by adhesion transfer (hereinafter referred to as a transfer method). The above-mentioned electrodeposition substrate is formed on a conductive substrate such as a metal plate with a pattern opposite to the mesh pattern made of an insulating film that inhibits electrodeposition. As a result, metal electrodeposition in a mesh shape is possible. It is produced so that a simple electrodeposition portion is exposed. When an electromagnetic shielding plate is produced by the transfer method using this electrodeposition substrate, it can be used repeatedly several times to several tens of times, but it cannot be used repeatedly several hundred times to several thousand times, and it can be used for mass production. There is a problem that must not be. This is because the insulating film forming the mesh pattern on the electrodeposition substrate is subjected to peeling stress by adhesion transfer, and the insulating film is peeled off from the electroconductive substrate for plating after a few repeated uses.

In the method described in Patent Document 1, generally, the step of performing metal electrodeposition and the step of blackening the surface of the deposited metal are separate steps.
When performing blackening treatment by causing copper-like metal to undergo oxidation of copper by electroplating, the deposition of black particles on the metal surface is likely to be excessive due to current concentration, Or it adheres and grows in the shape of a dendrite, and the omission of the black particle called the line thickening and also powder fall is easy to generate | occur | produce the whole mesh pattern or partially. These phenomena hinder the reduction of transmittance in applications that require transparency. On the contrary, if the current or voltage for the blackening process is insufficient, the degree of blackening is insufficient, and the overall color tone is reddish or partly red color irregularities are likely to occur.
In general, the solution used in the step of performing metal electrodeposition and the solution used in the step of blackening are different and are usually not allowed to mix with each other in the plating tank, and are performed in the same step. I can't. Therefore, sufficient water washing and further a blackening treatment pretreatment step may be required, and the time, cost, and environmental load required for production are not small.

  On the other hand, a metal foil such as iron, copper, chromium, nickel, or an alloy foil of these metals generally has a predetermined electrolyte solution containing ions of these metals between an insoluble cathode body and an insoluble anode body. The target metal is electrodeposited on the surface of the cathode body by a desired thickness by carrying out an electrolytic reaction while supplying a metal to form a metal conductor layer as a foil, and then the formed metal conductor layer is applied to the surface of the cathode body. Manufactured by peeling from. In this case, a drum-shaped or plate-shaped cathode body is used. By applying this manufacturing method, as shown in Patent Document 2, two or more anodes are arranged with respect to one drum-like cathode while using the same electrolyte bath, and the drum-like cathode is placed in the plating bath. After immersing about half and rotating the copper foil with the first current density, the second current density is applied and the copper on the fine particles is deposited on the surface, thereby the matte surface A method for producing a copper foil having a thickness of 2 is known. However, according to the knowledge of the present inventors, it is difficult to make the surface black or brown by the method of Patent Document 2.

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

  In view of the above problems, the present invention firstly provides a method for producing a metal pattern in which a metal having a geometric figure has a sufficient blackening degree or a more uniform blackening treatment in color tone or shape. Is. Secondly, the present invention provides a method for producing a metal pattern with higher productivity. Thirdly, this invention provides the manufacturing method of the base material with a conductor layer pattern including the manufacturing process of such a metal pattern. Fourthly, further, the present invention provides a method by which transfer can be performed more smoothly in a method for producing a substrate with a conductor layer pattern including a transfer step of a conductor layer pattern that has been blackened. It is. The present invention further provides a substrate with a conductor layer pattern and an electromagnetic wave shielding member using the same, which are obtained by such a method and have excellent electromagnetic wave shielding properties and light transmittance.

The present invention relates to the following.
1. In the method of manufacturing a metal pattern in which a metal is deposited on a conductive metal layer having a geometric diagram shape by a pulse electrolysis method and subjected to blackening treatment, the pulse electrolysis method has a high energization time T ₁ , the low power time and _{T 2,} 1 and 1 cycle cycle ₌ T 1 + _{T 2}
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
In this case, the process is performed under the condition that the cycle rate is maintained at 2% or more and 90% or less and each pulse energization time is maintained at 2 ms or more and 200 ms or less. Method.
2. Conductive layer formation for forming a conductive metal layer under a first current density in a method of manufacturing a metal pattern in which copper metal is deposited by electroplating on a conductive substrate for plating having a geometric pattern-shaped plated part pattern A step and a blackening treatment for depositing metal on the surface of the conductive metal layer under a second current density larger than the first current density so that the surface is black or brown; The manufacturing method of the metal pattern by which the process performed by a method was performed within the same plating bath, and the surface was blackened.
3. Item 3. The method for producing a metal pattern according to Item 2, wherein the plating part pattern is a concave pattern that is wide toward the opening direction.
4). In the pulse electrolysis method, the high energization time is T ₁ , the low energization time is T _2, and one cycle is one cycle = T ₁ + T ₂
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
The metal according to any one of Items 2 and 3, wherein the cycle rate is maintained at 2% or more and 90% or less and each pulse energization time is maintained at 2 ms or more and 200 ms or less. Pattern manufacturing method.
5. Item 1 in which the metal pattern whose surface has been blackened is blackened so that the brightness of the light transmitting part having an opening area of about 50% or more is 25 to 50 against a background of black having a lightness of 25 The manufacturing method of the metal pattern in any one of -4.
6). Item 6. The method for producing a metal pattern according to any one of Items 1 to 5, wherein in the blackening treatment step, each pulse electrolysis treatment is controlled by voltage.
7). A process for producing a metal pattern in which copper metal is deposited on a conductive substrate for plating having a plating part pattern having a geometrical shape by electroplating, and the metal deposited on the conductive substrate for plating is transferred to an adhesive support. In the method for manufacturing a substrate with a conductor layer pattern including a transfer step, the metal pattern manufacturing step includes a conductive layer forming step in which a conductive metal layer is formed under a first current density, and the first current density In the same plating bath, a step of performing blackening treatment by pulse electrolysis method for depositing metal on the surface of the conductive metal layer under a large second current density so that the surface becomes black or brown The manufacturing method of the base material with a conductor layer pattern characterized by performing.
8). Item 8. The method for producing a base material with a conductor layer pattern according to Item 7, wherein the plated portion pattern is a concave pattern that is wide toward the opening direction.
9. In the pulse electrolysis method, the high energization time is T ₁ , the low energization time is T _2, and one cycle is one cycle = T ₁ + T ₂
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
The conductor according to any one of Items 7 and 8, wherein the cycle rate is maintained at 2% or more and 90% or less and each pulse energization time is maintained at 2 ms or more and 200 ms or less. The manufacturing method of a base material with a layer pattern.
10. Item 7. Blackening the metal pattern whose surface is blackened so that the light-transmitting portion has a lightness of 25 to 50 with an opening area of about 50% or more against a black background of lightness 25 The manufacturing method of the base material with a conductor layer pattern in any one of -9.
11. Item 10. The method for producing a substrate with a conductor layer pattern according to any one of Items 7 to 10, wherein in the blackening treatment step, each pulse electrolysis treatment is controlled by voltage.
12 The base material with a conductor layer pattern manufactured by the method in any one of claim | item 7 -11.
13. Item 13. A light-transmitting electromagnetic wave shielding member obtained by bonding a surface having a conductor layer pattern of the substrate with a conductor layer pattern according to Item 12 to a transparent substrate.
14 Item 13. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 12 with a resin.

In the present invention, a blackened metal pattern having a sufficient degree of blackness or a more uniform color tone or shape by producing a blackened metal pattern using a pulse electrolysis method under specific conditions. Can be manufactured. (Excessive precipitation of blackened metal copper is suppressed, there is no thickening of the line, and no falling off of powder)
Further, according to the present invention, the conductive layer forming step and the blackening treatment can be performed in the same plating bath because the step of performing the blackening treatment by the pulse electrolysis method can be performed, so that a metal pattern that is well blackened is produced with high productivity. be able to.
In the present invention, the method for producing a substrate with a conductor layer includes the metal pattern production method described above, and thus has a blackened metal pattern with a sufficient degree of blackening or a more uniform color tone or shape. A substrate with a conductor layer pattern having good characteristics can be produced, and a substrate with a conductor layer pattern can be produced with good productivity.
In these methods, when the plated portion pattern is a concave pattern that is wide toward the opening direction, the metal pattern whose surface is blackened can be easily peeled off or transferred.
The electromagnetic wave shielding body obtained using the conductive layer pattern can be excellent in light transmittance. For this reason, when used as an electromagnetic wave shielding body of a display, a clear image can be comfortably viewed without adversely affecting the body due to electromagnetic waves without increasing the luminance. In addition, since the electromagnetic wave shielding body has excellent electromagnetic wave shielding properties, the display and other devices that generate electromagnetic waves, or measuring devices that are protected from external electromagnetic waves, measuring instruments and housings of manufacturing equipment, particularly transparency is required. It is very effective if it is used at a site such as a viewing window. Furthermore, the electromagnetic wave shielding body in the present invention can be produced with high production efficiency as in the case of the substrate with a conductor layer pattern.

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

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

In the present invention, the blackening process by plating using the pulse electrolysis method is performed on the conductive metal layer having the geometrical shape.
The geometrical-shaped metal layer may be formed on a conductive substrate for plating, or may be formed on a substrate such as a plastic film, a plastic plate, or a glass plate.
First, the geometrical figure-shaped metal layer formed on the conductive substrate for plating and the blackening treatment to the metal layer will be described.

  In the present invention, a metal layer (metal pattern) on a geometric figure can be produced by electrolytic plating or electroless plating on a conductive substrate for plating having a geometrically plated portion pattern. Said plating part pattern is formed of the convex part or recessed part formed in the electroconductive base material.

  The conductive substrate for plating in which the plating part is a recess will be described. It is preferable that an insulating layer is formed on the surface of the conductive base material, and a concave portion (plated portion) is formed in the insulating layer, and in particular, a concave portion for forming a wide plating in the opening direction ( Those having a plating part) are preferred. 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 is preferably in the range of 0.5 μm or more and 10 μm or less. The thickness of the insulating layer corresponds to the depth of the recess. Since the depth of the recess is also related to the thickness of the deposited plating, it is appropriately determined according to the purpose.
The thickness of the plating is preferably 0.5 μm or more, more preferably 3 μm or more in order to exhibit sufficient conductivity. Moreover, it is preferable to deposit the plating higher than the insulating layer by about 1 μm or more.
If the insulating layer is too thin, pinholes are likely to be generated in the insulating layer, so that when the plating is performed, the metal is likely to be deposited on the portion where the insulating layer is applied. The thickness of the insulating layer is particularly preferably 1 to 5 μm.

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

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

An example of the conductive substrate for plating will be described with reference to the drawings.
FIG. 1 is a partial perspective view showing an example of a conductive substrate for plating according to the present invention. FIG. 2 is a cross-sectional view taken along the line AA in FIG. FIG. 2A shows a case where the side surface of the concave portion, which is the plating portion, is a flat surface, while FIG. In the conductive base material 1 for plating, the insulating layer 3 is laminated on the conductive base material 2, and the concave portion 4 is formed in the insulating layer 3. Exposed. The bottom of the recess 4 may be a conductor layer made of a conductive material that is electrically connected to the conductive substrate.
In this example, the insulating layer 3 has a square shape as a geometric figure, and a recess 4 is formed in a groove shape around the square.
A conductive or insulating intermediate layer (not shown) may be laminated between the conductive substrate 2 and the insulating layer 3 for the purpose of improving the adhesiveness of the insulating layer 3 or the like. Alternatively, the recess 4 is wide as a whole in the opening direction. It is not always necessary that the width is constant and wide at the gradient α as shown in the drawing. If there is no problem in peeling of the 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.

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

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

  Further, the thickness of the insulating layer is the same as described above, but the depth of the concave portion 4 is preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm so as to correspond thereto. .

When the conductive substrate for plating 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 ′ 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.

  The concave portion of the conductive base material for plating corresponds to the shape of the metal pattern whose surface is blackened, and corresponds to the conductive layer pattern in the base material with a conductive layer pattern, and the conductive layer pattern. Corresponds to the electromagnetic wave shielding layer when the electromagnetic wave shielding member is finally produced.

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

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

The method for producing a conductive substrate for plating in the present invention includes a step of forming an insulating layer on the surface of the conductive substrate so that a geometrical figure is drawn by a recess exposing the conductive substrate. .
This step includes (A) a step of forming a removable convex pattern on the surface of the conductive substrate,
(B) 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 It can be produced by a method.

As the step of forming a removable convex pattern on the surface of the conductive substrate (A), a method of forming a resist pattern using a printing method or a photolithographic method can be used.
When using the photolithographic method, this method is
(A-1) forming a photosensitive resist layer on the conductive substrate;
(A-2) including a step of exposing the photosensitive resist layer through a mask corresponding to a concave pattern serving as a plating portion, and (a-3) a step of developing the exposed photosensitive resist layer (the above method “a method” ").

Moreover, the step of forming a removable convex pattern on the surface of the conductive substrate (A),
(B-1) a step of forming a photosensitive resist layer on the conductive substrate;
(B-2) a step of irradiating the photosensitive resist layer with a laser beam without masking a portion corresponding to the concave pattern serving as a plating portion; and (b-3) developing the photosensitive resist layer after the laser beam irradiation. Process (Process to remove unnecessary part of photosensitive resist)
(Referred to as “method b” above).

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

When the photolithographic method is used, the photosensitive resist layer can be formed by laminating a dry film resist on a conductive substrate. The photosensitive resist layer can be formed by applying a liquid resist and then drying or temporarily curing the solvent. The liquid resist can be applied by spraying, dispenser, dipping, roll, spin coating or the like.
From the viewpoint of productivity, the method of laminating a dry film resist and exposing it through a mask when the size of a plate is large or when it is produced by roll-to-roll (Roll-to-Roll), etc. Preferably, when processing directly on a plating drum or the like, a method of directly exposing with a laser or the like without using a mask after a dry film resist is bonded or a liquid resist is applied is preferable.

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

  Although a resist pattern (convex pattern) can be formed by using a printing method, in this case, various methods can be used as a method for printing a resist pattern. 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). For patterning, a photomask on which a pattern is formed is placed on the photosensitive resist layer 5, exposed, and then developed to remove unnecessary portions of the photosensitive resist layer 5 to leave the convex pattern 6. Is done. The convex pattern is considered to correspond to the concave portion 4 on the conductive substrate 2.

At this time, in the cross-sectional shape of the convex pattern 6, the side surface is perpendicular to the conductive substrate, or the convex pattern has a convex shape with respect to the end portion in contact with the conductive substrate 2. It is preferable that at least a part of the upper side surface of the pattern is positioned so as to cover the end. In terms of the width of the convex pattern, 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 recess width of the insulating layer having good adhesion is determined by d ₁ . Here, as a method of increasing the convex pattern width maximum value d _{1 in} the sectional shape of the convex pattern 6 to be equal to or larger than the width d ₀ in contact with the convex pattern and the conductive substrate 2, The resist may be over-developed at the time of development, or a resist having a characteristic that the shape is undercut. d ₁ is preferably is realized at the top of the convex portion.
When the conductive substrate for plating is used to prepare a conductor layer pattern for a light transmissive electromagnetic wave shielding member, the pattern shape of the removable convex portion is associated with the shape of the concave portion, but the maximum width It is preferable that it is 1-40 micrometers, a space | interval is 50-1000 micrometers, and height is 1-30 micrometers, respectively. In particular, it is preferable that the maximum width is 3 to 10 μm and the interval is 100 to 400 μm.

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

  As a method of forming a DLC thin film as an insulating layer, a dry vapor deposition method such as a vacuum vapor deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method, or a chemical vapor deposition method such as a plasma CVD method is employed. However, a high-frequency plasma CVD method in which the film formation temperature can be controlled from room temperature is particularly preferable.

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

  The insulating layer may be formed entirely by the above-described insulating DLC thin film, but it improves the adhesion of the DLC thin film to a conductive substrate such as a metal plate, thereby improving the durability of the insulating layer. In order to further improve, it is preferable to insert an intermediate layer composed of one or more components selected from Ti, Cr, W, Si, nitrides or carbides thereof, or the like, between the two.

  The Si or SiC thin film has excellent adhesion to, for example, a metal such as stainless steel, and also forms SiC at the interface with the insulating DLC thin film laminated thereon to improve the adhesion of the DLC thin film. Has the effect of improving.

  The intermediate layer can be formed by the dry coating method as described above.

  The thickness of the intermediate layer is preferably 1 μm or less, and more preferably 0.5 μm or less in consideration of productivity. A coating of 1 μm or more is not suitable because the coating time becomes long and the internal stress of the coating film increases.

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

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

  The insulating layer formed on the conductive substrate 2 and the insulating layer formed on the side surface of the convex pattern 6 are made to have different properties or characteristics. For example, the hardness of the former is greater than that of the latter. In this way, when the convex pattern is removed, the insulating layer is separated at this boundary. As a result, the inclination angle α of the side surface of the concave is preferably 30 degrees or more and less than 90 degrees, and preferably 30 degrees or more and 60 degrees. Degrees or less are particularly preferred. Such control can be easily performed when the DLC film is formed by plasma CVD, and it is easy to control the above angle to approximately 40 to 60 degrees. Accordingly, the recess 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 (convex pattern), 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 removing the convex pattern, the insulating layer (particularly the DLC film) is easily separated at this boundary. Further, the inclination angle α which 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 convex portion pattern with respect to the film thickness direction on the conductive substrate. Is controlled as described above.

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. An insulating layer having a hardness of less than 10 GPa is soft and has a low durability when repeatedly used as a conductive substrate for plating. A hardness of 40 GPa or more is not preferable because when the conductive substrate is processed such as bending, it cannot follow the deformation of the substrate and cracks and cracks occur in the insulating layer. More preferably, it is 12-30 GPa.
On the other hand, the hardness of the insulating layer formed on the side surface of the 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 them, and a wide concave portion is formed after a step of peeling off the convex pattern to which the insulating layer is attached later. As for the hardness of the insulating layer formed in a convex part side surface, it is more preferable that it is 1-10 GPa.
The hardness of the insulating layer can be measured using a nanoindentation method. In the nanoindentation method, a regular triangular pyramid (Berkovic type) indenter with a diamond tip is pressed into the surface of a thin film or material, and the hardness is obtained from the load applied to the indenter and the projected area under the indenter. As a measurement by the nanoindentation method, a device called a nanoindenter is commercially available. The hardness of the film formed on the conductive substrate can be measured by pressing an indenter from the conductive substrate as it is. In addition, in order to measure the hardness of the film formed on the side surface of the convex part, a part of the conductive substrate is cut out and cast with resin, and the indenter is pushed into the insulating layer formed on the side surface of the convex part from the cross section. Can be measured. Normally, in the nanoindentation method, the hardness is measured by applying a minute load of 1 to 100 mN to the indenter, but in the present invention, the value measured by applying a load of 3 mN for 10 seconds is described as the hardness value.
Thus, the electroconductive base material 1 for plating can be produced.

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

  In the conductive base material for plating according to the present invention, when the plating part pattern is a concave pattern, and the concave part becomes wider toward the opening direction, this is a convex shape that can be removed on the surface of the conductive base material. After the pattern is formed and the insulating layer is formed, it can be manufactured by removing the convex pattern to which the insulating layer is attached. Therefore, the manufacture is easy and the productivity is high. For the same reason, according to the method for producing a conductive substrate for plating of the present invention, the number of steps is small, and in particular, the plating part pattern is a concave pattern, and the concave part becomes wider toward the opening direction. In this case, since the concave portion can be easily produced, it can be produced with high production efficiency.

The electroconductive base material which a plating part consists of an electroconductive convex part pattern can also be used as an electroconductive base material for plating.
It is preferable that the width of the convex portion does not increase as the (exposed portion) advances in the tip direction, and that the width is smaller at the upper portion than at the lower portion as a whole. At this time, the concave portion corresponding to the convex portion is preferably covered with an insulating layer. Further, in this case, in the exposed portion of the convex portion, the end of the insulating layer on the side surface of the convex portion (first position) and the convex portion on the inner side in the width direction by an amount corresponding to 10% of the exposed width of the convex portion. The relationship d10 / h10 of the distance d10 in the width direction between the first position and the second position with respect to the distance h10 in the height direction from the surface position (second position) is 30 ° to 80 ° in angle. It is preferable to correspond. It is preferable that the width of the convex portion at a position 0.5 to 5 μm lower than the tip of the convex portion is 1 to 40 μm and the height of the convex portion exceeds 10 μm.

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

In the method (2), when a printing method is used, various methods can be used as a resist pattern printing method. For example, screen printing, letterpress printing, letterpress offset printing, letterpress reverse printing, intaglio printing, letterpress offset printing, ink jet printing, flexographic printing, and the like can be used. As the resist, a photocurable or thermosetting resin can be used.
In the case of using the photolithographic method, a dry film resist or the like is laminated, a mask is attached, exposed, developed, and then a resist film etching process can be performed. After drying or pre-curing, the resist film may be subjected to an etching process after being exposed by wearing a mask and developed. If the patterning can be performed by irradiating the photocurable resin with active energy rays through a mask, the mode is not limited. From the viewpoint of productivity, the method of laminating a dry film resist and exposing it through a mask when the size of a plate is large or when it is produced by roll-to-roll (Roll-to-Roll), etc. Preferably, when processing directly on a plating drum or the like, a method in which a dry film resist is bonded or a liquid resist is applied and then directly exposed with a laser or the like without using a mask is preferable.
Moreover, the etching of the base material in the method (2) can be performed using an etching solution. There are various types of etching solutions depending on the material of the substrate, and when etching solutions are commercially available for the respective substrates, they can be used. For example, if the base material is stainless steel, it is common to use ferric chloride, and if it is titanium, a hydrofluoric acid-based etching solution is often used. For the etching of stainless steel, a liquid having a specific gravity of ferric chloride in the range of 40 ° Be (Baume) to 60 ° Be (Baume) is preferably used. If the specific gravity is low, the etching speed is fast, but the side etching is large, so that the concave portion tends to become shallow. Conversely, if the specific gravity is high, the etching speed is slow, but the side etching is small and the concave portion tends to be deep. . Therefore, the specific gravity of the etching solution is more preferably 45 ° Be (Baume) to 50 ° Be. Further, if the etching temperature is low, the etching speed is lowered and the productivity is lowered. Therefore, the etching temperature is preferably 40 ° C. or higher. Furthermore, if the etching temperature exceeds 60 ° C., the corrosiveness of the etching solution increases, so that the equipment investment such as making the etching tank made of titanium increases.
The remaining resist can be stripped using a stripping solution or the like after etching the substrate.

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

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

Next, by performing dry etching on the insulating layer, the insulating layer formed at the tip portion of the convex portion can be removed, and thereby the tip portion of the convex portion can be exposed.
In particular, when plasma etching is performed with oxygen gas, the conductive base material becomes a stopper layer. When the convex part has a planar or substantially planar upper surface, if the insulating layer in the part exceeding the width of the upper surface of the convex part is exposed from the mask layer, the insulating layer can be removed by dry etching. Up to the side surface of the projection, and as a result, some of the side surface of the convex portion can be exposed. The removal of the insulating layer on the side surface can be controlled by the dry etching time and output.
Next, the mask layer formed on the recessed insulating layer 8 is removed by chemical solution immersion or the like. Thus, the electroconductive base material for plating which a plating part consists of a convex part pattern can be produced.

The mask layer can be broadly classified into inorganic and organic mask layers.
As the inorganic mask layer, metals such as aluminum (Al), chromium (Cr), nickel (Ni), cobalt (Co), gold (Au), and titanium (Ti) are particularly preferable because of their high resistance to oxygen plasma. Used. These films are formed by thin film forming methods such as sputtering, vacuum deposition, ion beam deposition, CVD, ion plating, electrodeposition, and electroless plating. Among these materials, aluminum (Al) is preferred because it is highly resistant to oxygen plasma, inexpensive, easy to deposit, and soluble in both acidic and basic substances. Used. Since aluminum is conductive, if it is left after dry etching, plating will be deposited on the entire surface of the conductive substrate, so it must be removed. Etching agents for aluminum include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate, etc. as basic substances, and sulfuric acid, persulfuric acid as acidic substances , Phosphoric acid, hydrochloric acid and salts thereof, etc., which are appropriately selected in consideration of the resistance of the insulating layer.

Further, as an inorganic material having resistance to oxygen plasma, when a wet coating method is used, a metal oxide polymer composed of alkali metal, organopolymetal, organoalkoxy metal, alkoxy metal, modified acetylacetonate metal, etc., inorganic A paint containing a filler and a paint made of silicon compound frit called a ceramic coating can be applied by spraying, dispenser, dipping, roll, spin coating or the like with a solvent such as alcohol or water added. Alternatively, a metal fluoride complex can be used as a mask layer on the insulating layer by a liquid layer deposition method (LPD method) or the like. It is also possible to form oxides of various metals by a dry coating method. As a coating method, it can be produced using a PVD method such as vapor deposition, sputtering, or ion plating, a CVD method such as plasma CVD or thermal CVD, or a method such as thermal spraying. Specifically, Al ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ , MgO, SiO, SiO ₂ , SnO ₂ , TaO ₅ , TiO ₂ , WO ₃ , Y ₂ O ₃ , ZnO, ZnO ₂ , ZrO A film such as ₂ is preferably used.

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

  In the present invention, in the blackening treatment in which the metal is deposited so that the surface of the metal becomes black or brown, a pulse electrolysis method is used, which is an energization method in which the current is periodically reduced or stopped for a certain time. Thereby, a black or brown-colored precipitation state can be favorably expressed.

As the plating bath used for the blackening treatment in the present invention, various plating solutions can be used. As an example, a copper plating bath such as a copper pyrophosphate bath or a copper sulfate bath can be used. The copper pyrophosphate bath is an electrolytic solution containing copper pyrophosphate and pyrophosphate. Specific examples thereof include those having the following composition.
Copper pyrophosphate 63-105 g / L (23-38 g / L as copper content)
Potassium pyrophosphate 200-470 g / L
As required, an aqueous solution in which ammonia water, potassium nitrate, a brightener and the like are dissolved and blended is used. For example, ammonia water having a specific gravity of 0.88 is used, preferably 1 to 6 mL / L, and potassium nitrate is preferably used in an amount of 8 to 16 g / L. Brighteners (mercaptothiazole, mercapto) It is preferable to use an appropriate amount of a thiazole-based additive.
In addition, sodium pyrophosphate and a commercially available additive for copper pyrophosphate plating can also be used. Furthermore, when one or more components of Group VI elements such as molybdenum and Group VIII elements such as cobalt and nickel are added to the plating bath, the blackening treatment can be performed more stably.
The copper sulfate bath is an electrolytic solution containing copper sulfate and sulfuric acid, and specific examples thereof include the following composition.
Copper sulfate (pentahydrate) 50-400 g / L (12-100 g / L as copper content)
Sulfuric acid 50-200 g / L
An aqueous solution in which chlorine ions and a surfactant are dissolved and blended is used as necessary.
Examples of the chlorine ion source include hydrochloric acid and sodium chloride, and it is preferable to use 20 to 100 mg / L. The surfactant is preferably used in an amount of 1 to 20 mL / L, and the brightener is preferably used in an amount of 0.1 to 10 mL / L. It is also possible to use high molecular polysaccharides and low molecular weight glues as chemicals instead of surfactants.

As the surfactant, an anionic, cationic, nonionic or amphoteric surfactant can be used. Nonionic surfactants are particularly preferable.
The nonionic surfactant is a concept that includes a polymeric surfactant, and includes, for example, polymeric surfactants such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, carboxymethyl cellulose, and polyacrylamide. In addition, such polymer surfactants include alkanols having 1 to 20 carbon atoms, phenols, naphthols, bisphenol compounds, alkylphenols having 1 to 25 carbons, arylalkylphenols, and alkyls having 1 to 25 carbons. Alkyl naphthol, alkoxylated phosphoric acid (salt) having alkyl having 1 to 25 carbon atoms, sorbitan ester, styrenated phenol, polyalkylene glycol, aliphatic amine having 1 to 22 carbon atoms, aliphatic having 1 to 22 carbon atoms An amide or the like may be obtained by addition-condensation of 2 to 300 moles of ethylene oxide or propylene oxide, or both.
Examples of cationic surfactants include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, Examples include trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, and octadecylamine acetate.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, (mono-, di- or tri-) alkyl naphthalene sulfonates. Etc. Examples of the alkyl sulfate include sodium lauryl sulfate and sodium oleyl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include sodium polyoxyethylene nonyl ether sulfate and sodium polyoxyethylene dodecyl ether sulfate. Examples of the polyoxyethylene alkylphenyl ether sulfate include polyoxyethylene nonylphenyl ether sulfate. Examples of the alkyl benzene sulfonate include sodium dodecylbenzene sulfonate. Examples of the (mono, di, tri) alkyl naphthalene sulfonate include sodium dibutyl naphthalene sulfonate.
Examples of the amphoteric surfactant include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Further, sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
Examples of the brightener include organic sulfur compounds. Examples of organic sulfur compounds include bis (3-sulfopropyl) disulfide, bis (2-sulfopropyl) disulfide, bis (3-sulfo-2-hydroxypropyl) disulfide, bis (4-sulfobutyl) disulfide, and bis (p-sulfo). Phenyl) disulfide, di-n-propyl-thioether-di-3-sulfonic acid, 3- (benzothiazolyl-2-thio) propylsulfonic acid, N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, O -Ethyl-diethyl carbonate-S- (3-sulfopropyl) ester, thiourea and its derivatives, S- (2-ethylamido) -thiopropanesulfonic acid, S- (3-propylamido) -thiopropanesulfonic acid, S -(4-Butylamide) -thiopropanesulfonic acid, S- (3-buty Amido) -thiopropanesulfonic acid, S- (3-propylamido) -thiopropyl-2-hydroxy-3-sulfonic acid, S- (3-propylamido) -thiophenylsulfonic acid, S- (N, N-dimethyl) -3-Propylamide) -thiopropanesulfonic acid, S- (N-phenyl-3-propylamido) -thiopropanesulfonic acid and the like, and salts thereof such as sodium salt and potassium salt.

  As the blackening treatment, plating treatment of other elements such as black nickel plating and cobalt plating can be performed.

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

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

For the production of a metal pattern that has not been blackened, and also in the conductive layer forming step of the metal pattern manufacturing process using a conductive substrate for plating, the metal pattern is formed by electroplating. The plating bath used in this case is preferably a copper plating bath such as the above-described copper pyrophosphate bath or copper sulfate bath.
As other plating baths, a watt bath, a sulfamic acid bath, and the like can be used as long as they are electrolytic nickel plating. In order to adjust the flexibility of the nickel foil in these baths, additives such as saccharin, paratoluenesulfonamide, sodium benzenesulfonate, sodium naphthalenetrisulfonate, and commercial additives that are their preparations, as needed An agent may be added. In the case of cobalt plating, there is a cobalt sulfate plating solution containing cobalt sulfate. Further, in the case of electrolytic gold plating, alloy plating using potassium gold cyanide, pure gold plating using an ammonium citrate bath or a potassium citrate bath, or the like is used. In the case of alloy plating, a gold-copper, gold-silver, gold-cobalt binary alloy or a gold-copper-silver ternary alloy is used. Similarly, other known methods can be used for other metals. As the electroplating method, for example, “Practical Plating for On-Site Engineers” (edited by Japan Plating Association, published by Sakai Shoten in 1986) pages 87 to 504 can be referred to.

The conductive metal layer having a geometric diagram shape can be manufactured by a conventionally known method.
The conductive metal layer having a geometrical shape is particularly preferably produced by plating using a conductive substrate for plating. This method is the same as the conductive layer forming step in the method of manufacturing a metal pattern whose surface is blackened using the conductive substrate for plating and including the conductive layer forming step and the blackening treatment step. However, the metal is not limited to copper metal. In such a method, electroplating is performed on the electroconductive substrate for plating under a specific current density applied between the electroconductive substrate for plating (cathode) and the anode (that is, the conductive substrate). A metal is deposited on the plated portion of the material) to form a conductive metal layer. The volume resistivity of the conductive metal layer is preferably 10 μΩ · cm or less, more preferably 5 μΩ · cm or less. The range of the specific current density is not more than the maximum current density indicating the upper limit of the current density for producing a normal film, and more than the critical current density which is the lower limit for producing a normal film. Specifically, it is affected by the composition of the electrolyte, the type and concentration of additives, the circulation method, the temperature, the stirring method, etc., and the plating part pattern is affected by whether it is a convex pattern or a concave pattern. However, it is generally not determined, but is preferably determined appropriately within the range of 0.5 A / dm ² or more and 60 A / dm ² or less. The reason is that a normal film cannot be obtained if the critical current density is exceeded. Prolonged needed to precipitate until the target thickness falls below 0.5A / dm ^2, results the production efficiency is not lowered production costs reduced, also is a precipitated copper exceeds 60A / dm ² not become normal film It interferes with subsequent processes such as transfer or peeling. From this viewpoint, the current density is preferably 40 A / dm ² or less.

  In the present invention, the manufacturing process of the metal pattern whose surface is blackened using the conductive substrate for plating includes a conductive layer forming step and a blackening treatment step, and these steps are respectively performed as separate plating baths or the same plating bath. Can be done in. The conductive layer forming step is as described above. Performing in the same plating bath is preferable for improving productivity.

  Among the methods including the blackening treatment of the conductive metal layer having a geometrical figure shape and the manufacturing process of the metal pattern having the blackened surface using the conductive substrate for plating, including the conductive layer forming step and the blackening treatment step The blackening process will be described.

A pulse electrolysis method is employed for the blackening treatment step in the present invention. This is a plating method in which high energization time and low energization time are alternately performed. High energization time is T ₁ , low energization time is T ₂ , 1 cycle is 1 cycle = T ₁ + T ₂
And the cycle rate E is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
If a high energizing time T ₁ and a low current supply time T ₂ are also the effect also or too long respectively too short is insufficient and may not be good blackening treatment, or excessive precipitation . When the pulse effect is insufficient, it is not sufficiently black, and on the contrary, when it is excessive, problems such as thickening of the black and powder fall off occur. In addition, an appropriate cycle is determined for the cycle rate in consideration of the current density. Desirable energizing time _{T 1} is at 2ms or 20ms or less, _{T 2} is 5ms or more and 200ms or less. More preferably, _{T 1} is 5 to 10 ms, _{T 2} is 50～100Ms. Moreover, a preferable cycle rate is 2% or more and 75% or less, More preferably, it is 5%-50%.
The current density at the time of high energization is made larger than the current density at the time of low energization, and the current density at the time of low energization is not applied (0 A / dm ² ) or larger than 0 A / dm ² . A current density within the range of the maximum current density during plating is desirable. The current density during high energization varies depending on the cycle rate and energization time for each cycle. As the tendency, the lower the cycle rate or the shorter the energization time, the higher the current density is required. On the contrary, when the cycle rate is high or the energization time is long, the current density under the direct current condition can be approached.
The upper limit of the current density during high current, it is preferable to 500A / dm ^2. Further, the current density during high energization is preferably 5 A / dm ² or more, more preferably 10 A / dm ² or more, higher than the current density during low energization.
The preferred current density varies depending on the pattern shape and area, various conditions such as plating solution temperature and solution agitation, and the conditions of T ₁ and T ₂ , but the preferred treatment time is determined.

In the method of manufacturing a metal pattern having a blackened surface using a conductive substrate for plating and including a conductive layer forming step and a blackening treatment step, the current density in the conductive layer forming step is the first current density, Assuming that the current density at the time of high energization in the blackening treatment process is the second current density, the second current density is the first current density when performing copper metal plating (particularly in the same copper plating bath). It is preferable to make it higher. The range of the second current density is equal to or higher than the maximum current density indicating the upper limit of the current density for generating a normal film, and the current replenishment of ions by diffusion reaches the limit, and the current density does not increase even when the voltage is increased. It is preferable that the density is not more than the limit current density indicating the maximum density. The appropriate value of the second current density varies depending on the mesh shape and other plating conditions, and thus cannot be generally specified, but is appropriately determined in consideration of the blackness. In some cases, the blackening process can be performed even when the second current density is 10 A / dm ² , and in some cases, the blacking process cannot be performed unless the current density is higher. In general, a finer pattern tends to require a larger current density. If the other conditions are the same, the second current density is generally appropriately selected from a range larger than the selected first current density. If the second current density is too large, the deposited metal tends to be needle-like deposited, which tends to cause defects such as transfer failure and powder fall. For this reason, the upper limit of the second current density is preferably 500 A / dm ² . Further, the second current density is preferably 5 A / dm ² or more higher than the first current density, and more preferably 10 A / dm ² or more. The second current density is not limited to one, and two or more may be changed stepwise to control the size of particles deposited as a blackened film.
The first current density is the same as the current density when the conductive metal layer having the above-described geometric diagram shape is produced by electroplating, and the current density during low energization in the blackening treatment step is 0 A / dm ^2. Or, it exceeds 0 A / dm ² and is below the maximum value of the first current density.

As described above, the formation method and the blackening treatment method have been described in the case where the conductive metal layer having the geometric diagram shape is formed on the conductive substrate for plating. The conductive metal layer having a geometrical shape formed by another method or formed on the conductive substrate for plating may be transferred to another substrate. The process is applied. In this case, the cycle _rate, T 1, _{T 2} are as above, a high current at a current density above the current density at low current (0A / dm ² except) 500A / dm ² or less in the range Preferably, the current density at low energization is preferably selected from the range of 0 A / dm ² or more than 0 A / dm ² and not more than 60 A / dm ^2, but smaller than the current density at high energization Is done. The current density at the time of low energization may be 0.5 A / dm ² lower than that at the time of high energization or may be 1 A / dm ² lower, and a current density suitable for the blackening process is selected.

In the blackening treatment step, fine particles of metal (especially, typically copper metal) are deposited on the surface of the conductive metal layer (especially, typically a copper metal layer) by electroplating, thereby black or It becomes brownish. This black or brown color is the appearance of fine particles deposited on the conductive metal layer underneath, and such fine particles are lined up on the conductive metal layer. It can be said that the black metal layer is formed by overlapping.
The purpose of blackening treatment is to cover the conductive metal layer with a black or brown metal layer, so in forming the conductive metal layer by plating, the current density is constant for the purpose of precipitating a predetermined film thickness. In other words, control by constant current is common, but when constant current control is applied to blackening treatment, the current density suitable for blackening treatment changes when the area to be plated changes, resulting in insufficient energization Or it tends to become excessive. Furthermore, since the appropriate range of blackening treatment varies depending on the shape of the object to be plated, plating solution composition, solution circulation, and temperature conditions, the current density management of blackening treatment generally requires delicate management and control. . In particular, in the case of continuous production in a roll shape or a hoop shape, the plating area changes periodically depending on the shapes of the conductive substrate and the insulating layer. Therefore, as a method for making a suitable current density constant, it is preferable that the blackening process is performed by control with a constant voltage or a substantially constant voltage. In the control with a constant voltage or a substantially constant voltage, the value of the current that flows mainly depends on the area to be plated, and as a result, it is possible to control with a substantially constant current density. The voltage during low energization is preferably in the range of 0 V or over 0 V to 3 V or less, and the voltage during high energization over the voltage during low energization to 10 V or less.

In order to quantitatively evaluate colors, numerical values are required, and several methods have been standardized by the International Commission on Illumination (CIE), but L * a * is a representative method. There is a b * color system. In this case, L * represents lightness, a * represents reddish green, and b * represents yellowish blue hue and saturation. L * is 0 for perfect black (total absorption of light), and 100 for perfect white (total reflection of light).
Substrates with a conductor layer pattern that shields the display surface of the display from electromagnetic waves are required to have good light transmittance. Therefore, it is preferable to reduce the coverage by the conductor layer pattern for shielding electromagnetic waves as much as possible, and to reflect external light. In order to enhance the brightness of transmitted light and improve the image quality, it is desirable that the conductor layer pattern itself be black. However, since the base material with a conductor layer pattern itself has high light transmittance, it is difficult to directly measure the chromaticity (brightness) of the fine conductor layer pattern itself. The same applies to the metal pattern whose surface has been blackened (hereinafter referred to as “blackened metal pattern”). Therefore, the brightness of the conductor layer pattern portion or the blackened metal pattern is measured against a black background of brightness 25. Specifically, the black surface of the conductor layer pattern or the blackened metal pattern is faced up, a black paper with a brightness of 25 is laid under the substrate with the conductor layer pattern, and the brightness is measured. If the conductive layer pattern is good black, the lightness L * is a value of 25 to 50, and the chromaticities a * and b * are both 5 or less. On the other hand, when the degree of black is insufficient and the original color of copper remains, the lightness L * is a high value of 60 or more, and both the chromaticities a * and b * are larger than 5 indicating redness or yellow.
The chromaticity can be measured by using a spectrocolorimeter CM-508d (Konica Minolta Holdings, Inc.) and setting the reflection mode. The colorimetric object part for measuring the brightness and chromaticity of this measuring device is a circle having a diameter of 8 mm, and the average color of the opening can be obtained.
In the present invention, the blackness in the blackening treatment is desirably completely black, but the blackened metal pattern, the conductor layer pattern, or the substrate with the conductor layer pattern and their uses (for example, an electromagnetic wave shielding member as a specific use) With the advancement of manufacturing technology and management technology in (or a filter or display device including the same), a blackened metal pattern or conductor layer pattern having a geometrical shape does not necessarily require a good black color, A dark color tone that can suppress reflection, that is, a brownish shade, may be used, and these evaluations can be performed as described above.

  In addition, when the conductive metal layer is formed and blackened using the conductive substrate for plating continuously, particularly in the same plating bath, it is washed with water between the conductor layer forming step and the blackening treatment step. Since the treatment and the surface treatment of the conductive metal layer are not required, the manufacturing time can be reduced and the cost can be reduced, and the environmental load can be reduced. Such a process is particularly useful when the metal is copper.

The metal thickness (plating thickness) deposited by plating on the plating portion of the conductive base material for plating is 0.5 μm in order to exhibit sufficient conductivity (at this time, sufficient electromagnetic shielding properties are exhibited). Preferably, the thickness is 3 μm or more in order to reduce the possibility of pinholes being formed in the conductor layer (in this case, the electromagnetic wave shielding property is lowered). Also, if the plating thickness is too large, the deposited metal spreads in the width direction, so the width of the transferred line becomes wider, the aperture ratio of the pattern base material with the conductor layer decreases, and transparency and invisibility are reduced. descend. Therefore, in order to ensure transparency and invisibility, the thickness of the deposited metal is preferably 20 μm or less. Further, in order to shorten the plating deposition time and increase the production efficiency, the thickness of the plating is preferred. Is more preferably 10 μm or less. The above plating thickness can be explained as the thickness of the conductive metal layer. The blackening process is performed using the lightness described above as a guide.
When using a conductive substrate for plating in which the plating part is a recess, in order to peel the plating film satisfactorily without disconnection or peeling failure through the adhesive or adhesive by the peeling substrate, the plating is an insulating layer. It is preferable to carry out so as to deposit the metal higher by about 1 μm or more. On the other hand, the thickness of the metal formed by plating from the viewpoint that the recessed portion becomes deeper relative to the thickness of the deposited metal layer, so that the deposited metal layer can be more shaped. Is preferably not more than twice the height of the insulating layer, particularly preferably not more than 1.5 times, and more preferably not more than 1.2 times, but is not limited thereto.
The degree of plating can be such that the deposited metal layer is present in the recess. Even in such a case, when the concave shape is wide in the opening direction, the surface of the concave side surface formed by the insulating layer can be smoothed. Can be made very small. Moreover, it becomes possible to make high the ratio of the height with respect to the width | variety of the metal layer to deposit, and to improve the transmittance | permeability more.

  A blackened metal pattern can be obtained by peeling off the blackened metal pattern formed on the conductive substrate for plating as described above by an ordinary method. In this case, as the substrate for peeling, a substrate in which an adhesive layer is laminated on another substrate is used, and the adhesive is directed to the surface of the conductive substrate for plating on which the blackened metal pattern is formed. Further, after the peeling substrate is pressure-bonded, it is peeled off, and the blackened metal pattern can be peeled off from the plating conductive substrate by transferring the blackened metal pattern to the peeling substrate. The blackened metal pattern is appropriately obtained by peeling from the peeling substrate.

  The blackened metal pattern in the present invention has a planar shape 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) hexagon, (positive) Metal foil with through-holes such as octagon, (positive) dodecagon, (positive) n-gon (n is an integer of 3 or more), circle, ellipse, star, etc. In order to make it easy to peel off from the conductive substrate for plating after plating, it is a continuous foil even if there is a through hole. It is preferable that The shape is selected according to the purpose. Such shapes can be used in combination. Further, the size and distribution density of the through holes or the recesses are appropriately determined according to the purpose. When a blackened metal pattern is produced using the above-described conductive substrate for plating, the shape thereof corresponds to the shape of the plated portion of the conductive substrate for plating.

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

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

In the present invention, the substrate with a conductor layer pattern is, for example,
(B) a step of forming a blackened metal pattern (conductor layer pattern) on the plating conductive substrate on the plating conductive substrate, and (b) a blackened metal pattern on the conductive conductive substrate for plating. Manufactured by a method including a step of transferring to a material.
The step (a) is as described above. Next, the process (b) will be described.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The above blackening treatment method is a method of forming a black layer on the conductor layer pattern (blackened metal pattern). For this purpose, various methods such as plating, oxidation treatment, and printing are used on the metal layer. be able to.

As the blackening treatment when the blackening treatment step is performed after transferring to another substrate, the above-described blackening treatment can be performed, but black plating such as black nickel plating can also be performed. The method described above can be used for black nickel plating. For the above, the method described above can be used. However, the current density is preferably from 0.5~3.0A / dm ^2.

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the electroconductive substrate for plating having the plating part pattern described in detail above, the plating part pattern is produced with an appropriate width.

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

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

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

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

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

  In the present invention, the conductor layer pattern produced on the conductive substrate for plating is transferred from the conductive support using an intermediate adhesive support by the same transfer method as described above. Further, the conductor layer pattern may be transferred from the intermediate adhesive support to the final adhesive support in the same manner as in the transfer method. In addition, an electromagnetic wave shielding body can be produced by stacking and pressing an intermediate adhesive support having a transferred conductor layer pattern and a final adhesive support with the conductor layer pattern interposed therebetween. Examples of the pressure bonding method in this case include a method of pressurizing with a press machine at room temperature or under heating, a method of passing between pressure rolls at room temperature or under heating, and the like.

  When the base material with a conductor layer pattern in the present invention is used as a shield, an antireflection layer, a near infrared shielding layer, or the like may be further laminated. The base material itself that transfers the metal deposited on the electroconductive base for plating may also serve as functional layers such as an antireflection layer and a near infrared shielding layer. Furthermore, the cover film used when the conductor layer pattern layer is coated with a resin may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.

  In addition to the electromagnetic wave shielding member, the substrate with the conductor layer pattern is 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, Application is possible as a member for light control film.

(Preparation of conductive substrate having convex pattern and concave portion of geometric diagram shape drawn thereby)
A resist film (Photech H-Y920, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 750 × 1100 mm stainless steel (SUS316L, finished 3 / 4H, thickness 0.3 mm, manufactured by Nisshin Steel Co., Ltd.) plate. The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, a negative film formed in a lattice shape with a line width of the light transmission portion of 30 μm, a line pitch of 300 μm, and a bias angle of 45 ° was left on a stainless steel plate to which a resist film was bonded. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above the negative film under a vacuum of 600 mmHg or less. Further, a resist mask having a line width of 30 μm, a line pitch of 300 μm, and a bias angle of 45 ° was formed on the SUS plate by developing with a 1% sodium carbonate aqueous solution. Furthermore, the SUS plate was etched using a ferric chloride aqueous solution (45 ° B, manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching was performed until the line width of the SUS plate became 20 μm. Next, using a 5% sodium hydroxide solution, the resist film formed on the SUS plate is peeled off to form a lattice pattern (line width, that is, the width of the upper surface of the convex portion is 20 μm, the pitch is 300 μm, the convex portion 15 μm in height, and the cross-sectional shape of the convex part is a curved surface (similar to FIG. 2 c), and has a pattern of convex part having an upper surface and a conductive base for plating having a concave part of the geometrical drawing shape drawn thereby. A material was prepared.

  In addition, the ground corresponding | compatible part (area | region B) of the mesh pattern of a convex part was formed in the outer peripheral part 40mm of the electroconductive base material for plating with the width | variety of the upper surface of a convex part 80 micrometers, a pitch 300 micrometers, and the height of a convex part 15 micrometers.

(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 plate with a resist film attached thereto was put 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 2 micrometers. At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 2 μm. The angle of the boundary surface was 45 to 51 degrees. In addition, the thickness of the insulating layer and the angle of the boundary surface were measured by cutting a part of the conductive base material and casting it with resin, and observing the cross section with SEM at a magnification of 3000 times. Since the measurement points were 5 points and both sides of the resist film were measured, a maximum value and a minimum value of 10 points in total were adopted.

(Concavity formation; removal of convex pattern with insulating layer attached)
The stainless steel plate with the insulating layer adhered 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.
As for the shape of the convex portion, the thickness of the DLC film at the upper end portion of the convex portion was 1.8 μm, and the thickness of the DLC film at the concave portion was 2 μm. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion. The pitch of the convex portions was 300 μm.

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

Drum diameter: 425mm
Drum width: 900mm
Plating tank: diameter 600mm, liquid capacity: 80L
Anode: Insoluble electrode plate Drum rotation speed: 0.4 rpm

The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.
Concentration of copper pyrophosphate: 100 g / L
Concentration of potassium pyrophosphate: 250 g / L
Ammonia water (30%) consumption: 2 mL / L
pH: 8-9
Bath temperature: 30 ° C
Anode: Titanium-based iridium oxide coating plate The plating bath was stirred only by gentle liquid circulation. The top surface of the convex portion of the conductive substrate was plated at a current density of 10 A / dm ² until the deposited metal thickness was 5 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. After that, as a constant current pulse energization process, the cycle rate (E) is set to 33% by setting the high energization condition to 150 A / dm ² , the low energization condition to 10 A / dm ^2, and the treatment time to 5 ms and 10 ms, respectively. Subsequently, plating was performed for 5 seconds to blacken the surface. The conductive substrate with the conductive pattern whose surface was blackened was taken out of the plating bath, washed with water, and dried.

(Preparation of adhesive film)
A 125 μm thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) is coated with a primer (HP-1, manufactured by Hitachi Chemical Co., Ltd.) with a thickness of 1 μm, and an acrylic as an adhesive layer. Polymers (HTR-280, manufactured by Nagase ChemteX Corporation) were sequentially applied to a thickness of 10 μm to prepare an adhesive film.

(Transcription)
The pressure-sensitive adhesive surface of this pressure-sensitive adhesive film and the surface having the copper plating in which the surface of the conductive base material was blackened were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C. and a pressure of 0.1 MPa. Subsequently, when the adhesive film bonded to the conductive substrate was peeled off, the copper deposited on the upper surface of the convex portion of the conductive substrate was transferred to the adhesive film.
Thereby, the base material with a conductor layer pattern which consists of a metal pattern with a line width of 28 μm, a line pitch of 300 μm, and a conductor thickness of 5 μm was obtained.
As a result of observing the conductive substrate after the transfer, there was no portion where the insulating film was peeled off.
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 base material with the conductor layer pattern obtained by the above blackening treatment is coated with UV curable resin Hitaroid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) and a polycarbonate film ( Macro hole DE, manufactured by Bayer Co., Ltd., 75 μm), the conductor layer pattern was embedded in the UV curable resin, and then irradiated with 1 J / cm ² of ultraviolet rays using an ultraviolet lamp to obtain the UV curable resin. It was cured to obtain a substrate with a conductor layer pattern having a protective film.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained substrate with a conductor layer pattern were measured using a spectrocolorimeter CM-508d (manufactured by Konica Minolta Holdings, Inc.). The measurement was performed in the reflection mode by placing black paper with a lightness L * = 25 on the lower part of the base material, and the SCI (including regular reflection light) method with a C light source of 10 ° (the same applies hereinafter).

  The object to be measured is an earth part formed outside the conductor layer pattern whose surface is blackened, and the opening area of the earth part is about 50%. As a result of the measurement, the lightness L * was 34, which was within a preferable range. The chromaticity was 0.4 for a * and 0.9 for b *, both of which were low in hue. The line shape of the conductor layer pattern was a good shape without black abnormal precipitation.

(Formation of convex pattern)
A resist film (Photech RY3525 (25 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 150 mm square titanium plate (mirror polished, thickness 0.5 mm, manufactured by Micron Industry Co., Ltd.). The conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min.Then, the line width of the light transmission part was 15 μm, the line pitch was 300 μm, and the bias angle was 45 ° (in a regular square, The negative film in which the line is arranged at an angle of 45 degrees with respect to the side of the regular square) and the pattern is formed in a grid shape with a size of 120 mm square is left on one side of the titanium plate. Using an ultraviolet irradiation device, ultraviolet rays were applied at 120 mJ / c from above and below the titanium plate on which the negative film was placed under a vacuum of 600 mmHg or less. ² was irradiated. In addition it is developed with 1% sodium carbonate aqueous solution to form a grid pattern consisting on the titanium plate line width 16～19Myuemu, line pitch 300 [mu] m, a resist film of the bias angle of 45 degrees. Incidentally, convex Since the entire surface opposite to the surface on which the partial pattern is formed is exposed, it is not developed and a resist film is formed on the entire surface.

(Formation of insulating layer)
An insulating film made of a DLC film was formed in the same manner as in Example 1.

(Concavity formation; removal of convex pattern with insulating layer attached)
The titanium substrate with the insulating layer adhered was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating (corresponding to FIG. 3D).
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 2 μm. Moreover, the width | variety in the bottom part of a recessed part was 16-19 micrometers, and the width | variety (maximum width) in an opening part was 21-27 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface on which the pattern of the conductive substrate for plating obtained above was not formed. Electrolytic copper plating was performed using the conductive substrate for plating with the adhesive film attached as a cathode. The bath composition of the electrolytic copper plating bath was the same as in Example 1.
The plating bath was stirred with gentle aeration. On the metal surface of the concave portion of the conductive substrate, plating was performed at a current density of 10 A / dm ² until the deposited metal thickness became 5 μm. The metal deposited at this stage was red, and the conductivity was 0.1Ω / □. After that, as a constant current pulse energization process, the high energization condition is 250 A / dm ² , the low energization condition is 10 A / dm ² , the treatment time is 10 ms and 60 ms, respectively, and the cycle rate (E) is set to 14%. Subsequently, plating was carried out for 10 seconds, and the conductive base material with the conductive pattern whose surface was blackened was taken out of the plating bath, washed with water, and dried.

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

(Transcription)
The surface of the pressure-sensitive adhesive layer of the transfer pressure-sensitive adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern whose line width is 20-25 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness is 5 micrometers on average was obtained. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.
As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off.

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

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained substrate with a conductor layer pattern were measured in the same manner as in Example 1.
The measurement target is a conductor layer pattern whose surface is blackened, and the opening area is about 80%. As a result of the measurement, the lightness L * was 40, which was within a preferable value range. Further, the chromaticity was 2.2 for a * and 1.7 for b *, and both values were low in hue.
The line shape of the conductor layer pattern was a good shape without black abnormal precipitation.

(Formation of convex pattern)
The resist film is Photec RY3415 (15 μm thick, manufactured by Hitachi Chemical Co., Ltd.), and the conductive substrate is coated on both sides of a 150 mm square titanium plate (# 400 polished finish, thickness 0.5 mm, manufactured by Micron Industry Co., Ltd.). They were pasted together (corresponding to FIG. 3 (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 mm square was left on one side of the titanium plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the titanium plate on which the negative film was placed under a vacuum of 600 mmHg or less. Further, by developing with a 1% sodium carbonate aqueous solution, a lattice pattern made of a resist film having a line width of 16 to 19 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was formed on the titanium plate. The width (d ₀ ) of the contact portion of the protrusion with the conductive substrate was 0 to about 1 μm smaller than this maximum width. Further, the minimum width of the protrusion is 0 to about 2 μm smaller than the maximum width (d ₁ ), and is a width at a slightly higher position from the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.
In addition, since the entire surface opposite to the surface on which the convex pattern is formed is exposed, the resist film is formed on the entire surface without being developed.

(Formation of insulating layer, formation of concave portion; removal of convex pattern with insulating layer attached)
An insulating layer made of a DLC film was formed in the same manner as in Example 2, and then the convex pattern was removed.

(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface on which the pattern of the conductive substrate for plating obtained above was not formed. Electrolytic copper plating was performed using the conductive substrate for plating with the adhesive film attached as a cathode. The bath composition and electrolysis conditions of the electrolytic copper plating bath are as follows.
Concentration of copper sulfate (pentahydrate): 200 g / L
Concentration of sulfuric acid: 100 g / L
Hydrochloric acid (35%) consumption: 0.2 mL / L
Additive: Microfil VF-AN (bis (3-sulfopropyl) disulfide salt; manufactured by Meltex Co., Ltd.) 0.3 mL / L
Microfil VF-BN (surfactant; manufactured by Meltex Co., Ltd.) 15 mL / L
Bath temperature: 25 ° C
Anode: Titanium-based platinum-coated plate The plating bath was aerated so that the solution was sufficiently stirred. On the metal surface of the concave portion of the conductive substrate, plating was performed at a current density of 10 A / dm ² until the thickness of the deposited metal reached 4 μm. The deposited metal at this stage was red, and the conductivity was 0.05Ω / □. Thereafter, the aeration is stopped to eliminate the liquid stirring, and then, as a constant current pulse energization process, the high energization condition is 85 A / dm ² , the low energization condition is 0 A / dm ^2, and the treatment time is 10 ms and 5 ms, respectively. Thus, the cycle rate (E) was set to 67%, and plating was continued for 5 seconds to blacken the surface. The conductive substrate with the conductive pattern whose surface was blackened was taken out of the plating bath, washed with water, and dried.

(Preparation of adhesive film for transfer)
A primer (HP-1, Hitachi Chemical Co., Ltd. thickness 1 μm) on the surface of a 100 μm thick polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) and acrylic as an adhesive layer Polymers (HTR-280, manufactured by Nagase Chemtech Co., Ltd.) were sequentially applied to a thickness of 10 μm to prepare a transfer adhesive film.

(Transcription)
The surface of the pressure-sensitive adhesive layer of the transfer pressure-sensitive adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 25 ° C., a pressure of 0.1 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive film. Thereby, the base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern whose line width is 20-25 micrometers, line pitch 300 +/- 2micrometer, and conductor layer thickness is 5 micrometers on average was obtained. The shape of the conductor layer reflects the shape of the concave portion, and as shown in FIG. 5 (h), the width is wide from the lower portion to the upper portion (adhesive layer), and the portion overflowing from the concave portion is like an umbrella. It has spread to.
As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating layer was peeled off.

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

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained substrate with a conductor layer pattern were measured in the same manner as in Example 1. The measurement target is a conductor layer pattern whose surface is blackened, and the opening area is about 85%. As a result of the measurement, the lightness L * was 43, which was within a preferable value range. The chromaticity was 1.1 for a * and 1.3 for b *, both of which were low in hue.
The line shape of the conductor layer pattern was a good shape without black abnormal precipitation.

(Preparation of conductive substrate having convex pattern and concave portion of geometric diagram shape drawn thereby)
The resist film is FOTEC RY3415 (15 μm thick, manufactured by Hitachi Chemical Co., Ltd.), and the conductive substrate is attached to a 750 × 1200 mm titanium plate (# 400 polished finish, thickness 0.5 mm, manufactured by Micron Industry Co., Ltd.). Combined. The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, a negative film in which the line width of the light transmission portion was 15 μm, the line pitch was 300 μm, the bias angle was 45 °, and the pattern was formed in a lattice shape was left on one side of the titanium plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the titanium plate on which the negative film was placed under a vacuum of 600 mmHg or less. Further, by developing with a 1% sodium carbonate aqueous solution, a lattice pattern made of a resist film having a line width of 16 to 19 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was formed on the titanium plate. The width (d ₀ ) of the contact portion of the protrusion with the conductive substrate was 0 to about 1 μm smaller than this maximum width. Further, the minimum width of the protrusion is 0 to about 2 μm smaller than the maximum width (d ₁ ), and is a width at a slightly higher position from the contact portion of the protrusion with the conductive substrate. These were measured by observing the cross section at a magnification of 3000 times with a scanning electron microscope (SEM). The number of measurement points was 5 or more.
In addition, since the entire surface opposite to the surface on which the convex pattern is formed is exposed, the resist film is formed on the entire surface without being developed.

(Formation of insulating layer)
A DLC film was formed in the same manner as in Example 1 except that the substrate was changed to a titanium plate.
At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 2 μm. The angle of the boundary surface was 45 to 51 degrees. In addition, the thickness of the insulating layer and the angle of the boundary surface were measured by cutting a part of the conductive base material and casting it with resin, and observing the cross section with SEM at a magnification of 3000 times. Since the measurement points were 5 points and both sides of the resist film were measured, a maximum value and a minimum value of 10 points in total were adopted.

(Concavity formation; removal of convex pattern with insulating layer attached)
The titanium plate with the insulating layer adhered 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).
As for the shape of the convex portion, the thickness of the DLC film at the upper end portion of the convex portion was 1.8 μm, and the thickness of the DLC film at the concave portion was 2 μm. This conductive substrate was covered with an insulating film except for the upper surface of the convex portion. The pitch of the convex portions was 300 μm.
(Copper plating)
Subsequently, the electroconductive base material which has an insulating film was fixed to the rotating drum electrode used as a cathode using a Teflon (trademark) tape, and electrolytic copper plating was performed with the same installation and bath as Example 1.
The plating energization treatment was performed under the following conditions.
On the metal surface of the concave portion of the conductive substrate, plating was performed at a current density of 8 A / dm ² until the thickness of the deposited metal reached 4 μm. Thereafter, as a constant voltage pulse energization process, the high energization condition is 7.5 V, the low energization condition is 0 V, the treatment time is 3 ms and 100 ms, respectively, and the cycle rate (E) is set to 3%, and then 5 Plating was performed for 2 seconds to blacken the surface. The conductive substrate with the conductive pattern whose surface was blackened was taken out of the plating bath, washed with water, and dried.
The production of the transfer adhesive film, the transfer and the protective film were processed in the same manner as in Example 2.

(Measurement of brightness and chromaticity)
The brightness and chromaticity of the obtained substrate with a conductor layer pattern were measured in the same manner as in Example 1. The measurement target is a conductor layer pattern whose surface is blackened, and the opening area is about 85%. As a result of the measurement, the lightness L * was 43, which was within a preferable value range. Further, the chromaticity was a * of 2.8 and b * of 2.2, both of which were low in hue.
The line shape of the conductor layer pattern was a good shape without black abnormal precipitation.

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

Explanation of symbols

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

Claims (14)

In the method of manufacturing a metal pattern in which a metal is deposited on a conductive metal layer having a geometric diagram shape by a pulse electrolysis method and subjected to blackening treatment, the pulse electrolysis method has a high energization time T ₁ , the low power time and _{T 2,} 1 and 1 cycle cycle ₌ T 1 + _{T 2}
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
In this case, the process is performed under the condition that the cycle rate is maintained at 2% or more and 90% or less and each pulse energization time is maintained at 2 ms or more and 200 ms or less. Method.   Conductive layer formation for forming a conductive metal layer under a first current density in a method of manufacturing a metal pattern in which copper metal is deposited by electroplating on a conductive substrate for plating having a geometric pattern-shaped plated part pattern A step and a blackening treatment for depositing metal on the surface of the conductive metal layer under a second current density larger than the first current density so that the surface is black or brown; The manufacturing method of the metal pattern by which the process performed by a method was performed within the same plating bath, and the surface was blackened.   The method for producing a metal pattern according to claim 2, wherein the plating part pattern is a concave pattern that is wide toward the opening direction. In the pulse electrolysis method, the high energization time is T ₁ , the low energization time is T _2, and one cycle is one cycle = T ₁ + T ₂
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
In this case, the cycle rate is maintained at 2% or more or 90% or less, and each pulse energization time is maintained at 2 ms or more and 200 ms or less. A method for producing a metal pattern.   The metal pattern whose surface is blackened is blackened so that the light transmitting portion having an opening area of about 50% or more has a lightness of 25 to 50 against a background of black having a lightness of 25. The manufacturing method of the metal pattern in any one of 1-4.   6. The method for producing a metal pattern according to claim 1, wherein in the blackening treatment step, each pulse electrolysis treatment is controlled by a voltage.   A process for producing a metal pattern for depositing copper metal by electroplating on a conductive substrate for plating having a geometric pattern-shaped plated part pattern, and transferring the metal deposited on the conductive substrate for plating to an adhesive support. In the method for manufacturing a substrate with a conductor layer pattern including a transfer step, the metal pattern manufacturing step includes a conductive layer forming step in which a conductive metal layer is formed under a first current density, and the first current density In the same plating bath, a step of performing blackening treatment by pulse electrolysis method for depositing metal on the surface of the conductive metal layer under a large second current density so that the surface becomes black or brown The manufacturing method of the base material with a conductor layer pattern characterized by performing.   Item 8. The method for producing a substrate with a conductor layer pattern according to Item 7, wherein the plated portion pattern is a concave pattern that is wide toward the opening direction. In the pulse electrolysis method, the high energization time is T ₁ , the low energization time is T _2, and one cycle is one cycle = T ₁ + T ₂
The cycle rate E in pulse electrolysis is defined as E = 100 × (T ₁ / (T ₁ + T ₂ ))
In this case, the cycle rate is maintained at 2% or more or 90% or less, and each pulse energization time is maintained at 2 ms or more and 200 ms or less. The manufacturing method of a base material with a conductor layer pattern.   The metal pattern whose surface is blackened is blackened so that the light transmitting portion having an opening area of about 50% or more has a lightness of 25 to 50 against a background of black having a lightness of 25. The manufacturing method of the base material with a conductor layer pattern in any one of 7-9.   The method for producing a substrate with a conductor layer pattern according to any one of claims 7 to 10, wherein in the blackening treatment step, each pulse electrolysis treatment is controlled by a voltage.   The base material with a conductor layer pattern manufactured by the method in any one of Claims 7-11.   The translucent electromagnetic wave shielding member formed by bonding the surface which has the conductor layer pattern of the base material with a conductor layer pattern of Claim 12 on a transparent substrate.   The translucent electromagnetic wave shielding member formed by coat | covering the conductor layer pattern of the base material with a conductor layer pattern of Claim 12 with resin.

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