JPH1056289A - Light transmissive electromagnetic wave shield material and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transmissive electromagnetic wave shield material and its manufacturing method wherein visibility is excellent and the effect of electromagnetic wave shielding is high. SOLUTION: With a polyester film of 100μm thickness as a transparent substrate 1, a copper foil of 35μm thickness is bonded on the transparent substrate 1 as a metal layer 2, and with photolithography, the metal layer 2 is patterned into a lattice of line thickness 10μm and scale division 100×100μm. Connected to a conductive line, it is submerged in an aqueous solution containing 1% of carbon black, 20% of aminate-epoxidized-polibutadiene (number average molecular weight about 1000), and 1% of triethylamine, and then applied with 10V for one minute to form a black electronic deposition layer 3 of 1μm thickness. The substrate is dried for 30 minutes at 60 deg.C, and then cooled down, and a film is laminated on it, so that a transmissive electromagnetic wave shield material is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-transmitting electromagnetic wave shielding material which functions to shield an electromagnetic wave and can see through the opposite side of the material, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Electronic devices such as computers in which ICs and LSIs are used in large quantities are apt to generate electromagnetic waves, and these electromagnetic waves cause malfunctions such as malfunctions of peripheral devices. In recent years, with the spread of devices related to electromagnetic wave interference and the influence of electromagnetic waves on the human body has been discussed, the demand for electromagnetic wave shielding materials has been increasing.

Some electromagnetic wave shielding materials not only function to shield electromagnetic waves, but also, for example, can be used as a front panel of a display or a microwave oven window so that they can be used as a window of a microwave oven. Some are translucent so that the back of the material can be seen. In particular, when a front panel such as a display is used, a display screen is viewed through an electromagnetic wave shielding material. Therefore, a display screen having excellent visibility while maintaining electromagnetic wave shielding properties is desired.

Conventionally, it has a function of shielding electromagnetic waves,
As a translucent electromagnetic wave shielding material that can see through the opposite side of the material, 1) a material in which a conductive net is sandwiched between glass or transparent resin plates, or a conductive net is embedded in a glass or transparent resin plate, 2) There is a case where a transparent conductive thin film such as gold or ITO is formed on a glass or transparent resin plate by vapor deposition or sputtering. In the case of the translucent electromagnetic wave shielding material of 1), the conductive net surface is dyed black to suppress the reflection on the net surface in order to enhance the visibility.

[0005]

However, in the case of the light-transmitting electromagnetic wave shielding material of 1), the conductive net is formed by plating a wire mesh or a woven fiber or a knitted fiber having a standard such as a line width and a pitch. , The design of the line width and pitch of the net was severely restricted.
For this reason, a conductive net cannot be obtained with a design that is optimal in terms of visibility and electromagnetic wave shielding effect, and visibility is poor,
The electromagnetic wave shielding effect was low.

In the case of the light-transmitting electromagnetic wave shielding material 2), visibility is poor due to the metallic luster of the gold film.
Since the TO film has low conductivity, the electromagnetic wave shielding effect was low.

Accordingly, an object of the present invention is to provide a translucent electromagnetic wave shielding material having excellent visibility and a high electromagnetic wave shielding effect, and a method for producing the same.

[0008]

In order to achieve the above-mentioned object, a light-transmitting electromagnetic wave shielding material according to the present invention has a metal layer laminated on a transparent substrate in a pattern, and the metal layer is registered on the metal layer. It was configured such that the matched black electrodeposition layers were laminated.

The black electrodeposition layer may be laminated so as to be in register with the metal layer except for the ground portion.

In each of the above structures, the black electrodeposited layer may be a layer containing black particles in an ionic polymer, a layer made of a black conductive polymer, or an electroplated film having a black color tone. It consisted of. As the above-mentioned ionic polymer, an acrylic resin, a polyester resin, a polybutadiene resin, a maleic resin, an epoxy resin, a urethane resin, a polyamide resin or a modified product thereof, which is aminated or carboxylated, can be used. In addition, carbon black, titanium black, and aniline black can be used as the black particles.
Further, as the conductive polymer, a polymer of pyrrole, aniline, thiophene, and a derivative thereof can be used. Further, the electroplating film having the black color tone may be a nickel-based, chromium-based, rhodium-based, tin-nickel-copper ternary alloy-based, or tin-nickel-molybdenum ternary alloy-based.

According to the method for producing a light-transmitting electromagnetic wave shielding material of the present invention, a step of laminating a metal layer in a pattern on a transparent substrate and a step of laminating the metal layer in a solution of an ionic polymer containing black particles in a preceding step are performed. The transparent substrate on which was laminated was immersed together with the counter electrode, and a current was applied to the transparent substrate to laminate the black electrodeposition layer on the metal layer.

The method for producing a light-transmitting electromagnetic wave shielding material according to the present invention includes a step of laminating a metal layer on a transparent substrate in a pattern, and a step of forming a metal layer in a solution of a monomer of a conductive polymer in a previous step. The laminated transparent substrate was immersed together with the counter electrode and energized to form a black electrodeposition layer on the metal layer.

The method for producing a light-transmitting electromagnetic wave shielding material according to the present invention comprises a step of laminating a metal layer in a pattern on a transparent substrate, and a method of forming an electroplating film having a black color tone in a plating solution. The transparent substrate on which the metal layer was laminated in the previous step was immersed together with the counter electrode and energized to form a step of laminating a black electrodeposition layer on the metal layer.

In each of the above-described manufacturing methods, a mask layer is laminated on a part of the patterned metal layer before the black electrodeposition layer is laminated, and the black electrodeposition layer is laminated on the mask layer. After that, the mask layer may be removed and the exposed portion of the metal layer may be used as a ground portion.

Alternatively, in each configuration according to the above-described manufacturing method, a black electrodeposition layer is laminated on a patterned metal layer without using a mask layer, and then a part of the black electrodeposition layer is removed to expose the metal layer. The part that has been set may be used as a ground part.

In each of the above structures, a step of laminating a metal layer over the entire surface of the transparent substrate, a step of laminating a positive resist layer on the metal layer in a pattern, and a step of covering with a positive resist layer. After the step of removing the metal layer of the non-existing part by etching, the step of exposing and developing the positive resist layer while leaving a part, a black electrodeposition layer is laminated on the metal layer, and the remaining positive resist layer And the exposed portion of the metal layer may be used as a ground portion.

[0017]

Embodiments of the present invention will be described below in more detail with reference to the drawings. FIGS. 1, 8, 10, and 12 are schematic diagrams showing one embodiment of a manufacturing process of the translucent electromagnetic wave shielding material of the present invention, and FIGS. 2 to 5 show one embodiment of a pattern of a black electrodeposition layer. FIG. 6, FIG. 6, FIG. 9, FIG. 11, and FIG. 13 are schematic diagrams showing an apparatus for depositing a black electrodeposition layer on a metal layer according to the present invention, and FIG. 7 is one example of a translucent electromagnetic wave shielding material having an earth portion. It is a schematic diagram which shows an Example. 1 is a transparent substrate, 2 is a metal layer, 3 is a black electrodeposition layer, 4 is a counter electrode, 5 is a ground portion, 6 is a translucent electromagnetic wave shield portion, 7 is a mask layer, and 8 is a positive resist layer. .

In the manufacturing process of the translucent electromagnetic wave shielding material shown in FIG. 1, first, a metal layer 2 is provided on a transparent substrate 1 in a pattern (see FIG. 1A).

The material of the transparent substrate 1 includes glass, acrylic resin, polycarbonate resin, polyethylene resin, AS resin, vinyl acetate resin, polystyrene resin, polypropylene resin, polyester resin, polysulfone resin, polyethersulfone resin, and polychlorinated resin. What is necessary is just to be transparent like vinyl. Further, the transparent substrate 1 is a plate,
There are films.

The material of the metal layer 2 is, for example, gold,
Use a conductive material such as silver, copper, iron, nickel, and chromium that can sufficiently shield electromagnetic waves. Further, the metal layer 2 is not limited to a simple substance, but may be an alloy or a multilayer. Examples of the method of forming the metal layer 2 include a method of depositing from a gas phase such as vapor deposition, sputtering, and ion plating, a method of attaching a metal foil, and a method of electrolessly plating the surface of the transparent substrate 1. It is preferable that the thickness of the metal layer 2 be 0.1 μm to 50 μm. 50μ
If it exceeds m, it becomes difficult to finish the pattern with high accuracy, and if it is less than 0.1 μm, it becomes impossible to stably secure the minimum necessary conductivity for maintaining the electromagnetic wave shielding effect.

As a method for patterning the metal layer 2, there is a method in which the metal layer 2 is provided on the entire surface of the transparent substrate 1, and the metal layer 2 is subjected to photolithography or the like. Alternatively, a pattern of a conductive metal film may be formed in advance, and the pattern may be bonded to the transparent substrate 1. The pattern of the metal layer 2 has, for example, a lattice shape (see FIG. 2), a honeycomb shape (see FIG. 3), a ladder shape (see FIG. 4), a reverse polka dot shape (see FIG. 5), and the like.

Next, on the patterned metal layer 2, a black electrodeposition layer 3 which is in register with the metal layer 2 is laminated (see FIG. 1b).

The black electrodeposition layer 3 is a layer for suppressing the reflection on the surface of the metal layer 2 to enhance visibility, and for example, there is a layer in which black particles are contained in an ionic polymer.
In order to laminate such a black electrodeposition layer 3, the transparent substrate 1 on which the metal layer 2 has been laminated in the previous step is immersed in a solution of an ionic polymer containing black particles together with the counter electrode 4 and energized. Good (see Figure 6).

As the black particles, carbon black,
There are titanium black, aniline black and the like. Also,
Instead of the black-based particles, some particles other than the black-based particles may be combined to have a substantially black-based appearance.
Note that the black type in the present invention includes, besides pure black, for example, a dark brown or a dark green. As the ionic polymer, an acrylic resin, a polyester resin, a polybutadiene resin, a maleic resin, an epoxy resin, a urethane resin, a polyamide resin or a modified product thereof, which is aminated or carboxylated, is used. The content of these ionic polymers in the aqueous solution is 1 solid content.
-30 parts by weight. In addition, additives such as inorganic salts, organic salts, surfactants, and organic solvents are used to stabilize the conditions at the time of energization and to improve the conductivity and mechanical surface properties of the black electrodeposition layer 3. May be added to the solution of the conductive polymer.

Electric current is applied to the metal layer 2 laminated on the transparent substrate 1.
Is exposed from the liquid interface or a lead wire coated with insulation is connected, and a voltage of 1 to 300 V may be applied to the counter electrode 4.

The black electrodeposition layer 3 may be made of a black conductive polymer. In order to laminate such a black electrodeposited layer 3, the transparent substrate 1 on which the metal layer 2 has been laminated in the previous step is immersed in a solution of a monomer of a conductive polymer together with the counter electrode 4 and energized (FIG. 6). This is so-called electrolytic polymerization.

The monomer of the conductive polymer is selected from pyrrole, aniline, thiophene and derivatives thereof. Examples of the solvent for dissolving the monomer include water, acetonitrile, propion carbonate, tetrahydrofuran, nitromethane, methanol, ethanol, and sulfolane.

In order to stabilize the current supply and perform electrochemical doping, a dopant is added to the solution of the conductive polymer monomer in the solution. Examples of the dopant include lithium perchlorate, tetraalkylammonium borofluoride, and sulfuric acid. Furthermore, the black electrodeposition layer 3
In order to more stably form GaN, it is desirable to control the potential using a reference electrode. Further, as a method of energization, there is a method of periodically increasing and decreasing the potential, in addition to the constant potential electrolysis method and the constant current electrolysis method.

The color of the deposited conductive polymer exhibits various colors depending on the conditions at the time of energization, the degree of polymerization, the type of monomer, etc., but is generally black and suppresses reflection on the surface of the metal layer 2. be able to. The thickness of the black electrodeposition layer 3 is
The thickness is preferably 0.1 μm to 10 μm. If it exceeds 10 μm, it becomes difficult to finish the above pattern with high accuracy, and if it is less than 0.1 μm, sufficient light-shielding properties cannot be maintained and it is difficult to suppress reflection on the surface of the metal layer 2.

As the black electrodeposition layer 3, in addition to the above two examples, a black electrodeposition layer 3 composed of charged black particles or a solution containing black particles in micelles in the production process is used. It is expected that things will be obtained.

As the black electrodeposition layer 3, an electroplating film having a black color tone may be used. In order to laminate such a black electrodeposited layer 3, the transparent substrate 1 on which the metal layer 2 has been laminated in the previous step may be immersed in an electroplating solution for forming a film having a black color tone, and then energized. (See FIG. 6).

As the electroplated film having a black color tone, a nickel-based, chromium-based, rhodium-based, tin-nickel-copper ternary alloy-based or tin-nickel-molybdenum ternary alloy-based one can be used. . Note that the black type in the present invention includes, besides pure black, for example, a dark brown or a dark green.

As a method of electroplating, for example, a method in which a transparent substrate 1 on which a metal layer 2 is laminated is placed in a rack or hung, dipped, and energized to perform plating, or a plating solution is deposited on a metal layer 2 from a spray nozzle. There is a method of plating while energizing while spraying the transparent substrate 1 thus formed. In the case where the transparent substrate 1 on which the metal layer 2 is laminated is in the form of a film that can be wound, a continuous (hoop) plating method can be used.

The color tone of the deposited electroplated film slightly varies depending on the conditions at the time of energization, the composition of the plating solution components, and the like.
Basically, it is a black type, and can suppress reflection on the surface of the metal layer 2. The thickness of the black electrodeposition layer 3 is 0.1 μm
The thickness is preferably from 10 to 10 μm. If it exceeds 10 μm, it becomes difficult to finish the above pattern with high precision,
If it is smaller than μm, sufficient light-shielding properties cannot be maintained, and it is difficult to suppress reflection on the surface of the metal layer 2.

If the metal layer 2 and the black electrodeposition layer 3 formed on the transparent substrate 1 in this manner are weak in strength, the side where the metal layer 2 and the black electrodeposition layer 3 are formed may be provided if necessary. The protective layer may be provided by coating or film lamination. As the material of the protective layer, various functions can be included in the protective layer, for example, a non-glare function, an antistatic function, an anti-Newton ring function, and the like.Therefore, a material according to each function may be selected, and there is no particular limitation. . Also,
The translucent electromagnetic wave shielding material of the present invention is usually used so as to be seen through from the surface on which the metal layer 2 and the black electrodeposition layer 3 of the transparent substrate 1 are laminated, but is thin enough to have transparency. When formed, it can be used so as to be seen through from the transparent substrate 1 side.

The translucent electromagnetic wave shielding material needs to be grounded, and there are various means, but it is most preferable to partially expose the metal layer 2 on the surface where the black electrodeposition layer 3 of the shielding material is formed. Easy. That is, the transparent substrate 1
The translucent electromagnetic wave shielding material is configured such that the metal layer 2 is laminated on the metal layer 2 in a pattern, and the black electrodeposition layer 3 which is aligned with the metal layer 2 except for the ground portion 5 is laminated on the metal layer 2. I do. The grounding portion 5 includes, for example, a frame portion (see FIG. 7) surrounding the translucent electromagnetic wave shield portion 6 and a rod-shaped portion adjacent to an end of the translucent electromagnetic wave shield portion 6.

In order to manufacture a light-transmitting electromagnetic wave shielding material having the ground portion 5, a process as shown in FIGS.

In the manufacturing process of the translucent electromagnetic wave shielding material shown in FIG. 8, first, the metal layer 2 is laminated on the transparent substrate 1 in a pattern (see FIG. 8A).

Next, a mask layer 7 is laminated on a part of the metal layer 2 (see FIG. 8B). The mask layer 7 is a layer that protects a portion of the metal layer 2 serving as the ground portion 5 from being etched when the metal layer 2 is patterned, and that is removed after patterning is completed. For the mask layer 7, a printing resist or a photoresist material which is generally commercially available is used. The mask layer 7 may be formed on a part of the metal layer 2 by a screen printing method using a printing resist material,
Using a photoresist material, a solid coating is formed on the metal layer 2 by a roll coating method, a spin coating method, a full-surface printing method, a transfer method, and the like, and is exposed using a photomask,
It is partially formed by development.

Next, after laminating the black electrodeposition layer 3 on the metal layer 2 (see FIG. 8C), the mask layer 7 is removed and the exposed portion of the metal layer 2 is used as the ground part 5 (see FIG. 8D). ).
As a result, a translucent electromagnetic wave shield in which the metal layer 2 is laminated on the transparent substrate 1 in a pattern, and the black electrodeposition layer 3 which coincides with the metal layer 2 except for the ground portion is laminated on the metal layer 2. The material is obtained. As a method for removing the mask layer 7, for example, there is a method for dissolving and removing with a stripping solution. FIG. 9 shows the black electrodeposition layer 3 in this method.
This is a deposition device for stacking.

In the manufacturing process of the light-transmitting electromagnetic wave shielding material having the ground portion 5 shown in FIG. 10, the ground portion 5 is formed without using the mask layer 7. That is, the metal layer 2 is laminated in a pattern on the transparent substrate 1 (FIG. 10A).
After the black electrodeposition layer 3 is laminated on the metal layer 2 (see FIG. 10B), a part of the black electrodeposition layer 3 is removed and the exposed portion of the metal layer 2 is used as a ground portion 5 (see FIG. 10B). 10c
reference). As a method for removing a part of the black electrodeposited layer 3, for example, there is a method in which the black electrodeposited layer is adhered to an adhesive tape or the like, and a method in which it is mechanically scraped off. Note that FIG.
Is a deposition apparatus for laminating the black electrodeposition layer 3 in this method.

The manufacturing process of the light-transmitting electromagnetic wave shielding material having the ground portion 5 shown in FIG. 12 is performed by processing the positive resist layer 8 used in the step of laminating the metal layer 2 on the transparent substrate 1 in a pattern. Then, the mask layer 7 is used instead. That is, the metal layer 2 is laminated on the entire surface of the transparent substrate 1 (see FIG. 12A), the positive resist layer 8 is laminated on the metal layer 2 in a pattern (see FIG. 12B), and then covered with the positive resist layer 8. The remaining metal layer 2 is removed by etching (see FIG. 12C). Next, the positive resist layer 8 is removed by exposure and development while leaving a part (see FIG. 12d), and after the black electrodeposition layer 3 is laminated on the metal layer 2 (see FIG. 12e), the remaining positive resist is removed. Layer 8
Is removed to make the exposed portion of the metal layer 2 a ground portion 5 (see FIG. 12F). FIG. 13 shows a deposition apparatus for laminating the black electrodeposition layer 3 in this method.

[0043]

【Example】

Example 1 A metal layer of a polyester film having a thickness of 100 μm to which a copper foil having a thickness of 35 μm was bonded was patterned by photolithography into a lattice shape having a line width of 10 μm and a mesh size of 100 × 100 μm. A conductive wire was connected to this, immersed in an aqueous solution containing 1% of carbon black, 20% of aminated epoxidized polybutadiene (number-average molecular weight: about 1000), and 1% of triethylamine. A 1 μm black electrodeposition layer was formed. This substrate is
After drying at 30 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a translucent electromagnetic wave shielding material.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 2 A polymethyl methacrylate film having a thickness of 100 μm was used as a transparent substrate, and a metal layer having a thickness of 0.2 μm was formed on one side of the film by nickel vapor deposition. This metal layer was patterned into a honeycomb shape having a line width of 20 μm and an eye diameter of 200 μm by photolithography. A conductive wire was connected to the metal layer, immersed in an aqueous solution containing 1% of carbon black, 15% of maleated polybutadiene and 1% of triethylamine, and a voltage of 30 V was applied for 5 minutes to form a black electrodeposited layer having a thickness of 1 μm. Formed. This substrate was dried at 60 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 3 An acrylic plate having a thickness of 3 mm was used as a transparent substrate, and an acrylic resin (BR-77 manufactured by Mitsubishi Rayon Co., Ltd.) was applied on one surface of the plate and immersed in 1% potassium hydroxide for 5 minutes. / Tin chloride colloid solution, dipped in 1% potassium hydroxide for 1 minute, and subjected to electroless nickel plating. Next, the metal layer is formed with a line width of 30 by photolithography.
The pattern was formed into a grid having a size of 150 μm and a mesh size of 150 × 150 μm. A conductive wire is connected to this metal layer, immersed in an aqueous solution containing 1% of titanium black, 20% of aminated epoxidized polybutadiene and 1% of triethylamine, and applied with a voltage of 30 V for 3 minutes to give a black electrodeposit of 1 μm in thickness. A layer was formed. This substrate was dried at 60 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 4 A metal layer of a borosilicate glass plate having a thickness of 1.1 mm on which nickel having a thickness of 0.3 μm was vapor-deposited was patterned by photolithography into an inverted polka dot shape having an inner diameter of 100 μm and a pitch of 110 μm. A conductive wire was connected to this metal layer, and further immersed in an acetonitrile solution containing 0.5 M of pyrrole, 0.5 M of sulfuric acid, and 0.2 M of tetraethylammonium borofluoride, and a platinum plate as a counter electrode and a saturated calomel electrode as a reference electrode. The electrode was placed and energized at 0.8 V vs. SCE for 3 minutes to form a black electrodeposited layer having a thickness of 1 μm. Then at 60 ° C 3
After drying for 0 minutes and cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material.

The translucent electromagnetic wave shielding material thus obtained was excellent in visibility and high in the shielding effect.

Example 5 A metal layer of a polyester film having a thickness of 100 μm to which a copper foil having a thickness of 35 μm was bonded was patterned by photolithography into a lattice shape having a line width of 10 μm and a mesh size of 100 μm × 100 μm. A conductive wire was connected to this, and nickel sulfate 70 g / l and nickel ammonium sulfate 40 g /
1, zinc sulfate 20 g / l, sodium thiocyanate 20
g / l of plating solution at 55 ° C containing 1 A / d
A current of m ² was applied for 3 minutes to form a black electrodeposited layer. This substrate was dried at 60 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material having an electroplating film having a black color tone.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 6 A 100 μm thick polymethyl methacrylate film was used as a transparent substrate, and a metal layer having a thickness of 0.2 μm was provided on one side of the film by nickel vapor deposition. This metal layer was patterned into a honeycomb shape having a line width of 20 μm and an eye diameter of 200 μm by photolithography. A conductive wire was connected to this metal layer, and 200 g / l of chromium trioxide and 4.5 g of barium acetate were used.
/ L and 8.5 g / l of sodium nitrate were immersed in a plating solution at 30 ° C, and a current of 100 A / dm ² was applied for 5 minutes to form a black electrodeposited layer having a thickness of 1 µm. This substrate was dried at 60 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material having an electroplating film having a black color tone.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 7 An acrylic plate having a thickness of 3 mm was used as a transparent substrate, an acrylic resin (BR-77, manufactured by Mitsubishi Rayon Co., Ltd.) was applied on one surface thereof, immersed in 1% potassium hydroxide for 5 minutes, and then palladium chloride. / Tin chloride colloid solution, dipped in 1% potassium hydroxide for 1 minute, and subjected to electroless nickel plating. Next, the metal layer is formed with a line width of 30 by photolithography.
The pattern was formed into a grid having a size of 150 μm and an eye size of 150 × 150 μm. A conductive wire was connected to the metal layer, immersed in a plating solution at 25 ° C. having a rhodium concentration of 3.0 g / l and a sulfuric acid concentration of 27 g / l, and subjected to a current of 4 A / dm ² for 5 minutes. A black electrodeposited layer of 4 μm was formed. 6
After drying at 0 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material having an electroplated film having a black color tone.

The light-transmitting electromagnetic wave shielding material obtained in this manner had excellent visibility and a high shielding effect.

Example 8 A metal layer of a borosilicate glass plate having a thickness of 1.1 mm on which nickel having a thickness of 0.3 μm was vapor-deposited was patterned by photolithography into an inverted polka dot shape having an inner diameter of 100 μm and a pitch of 110 μm. A conductive wire is connected to this metal layer, and potassium pyrophosphate 200 g / l, tin pyrophosphate 15 g / l, nickel sulfate 15 g / l, sodium molybdate 105
The electrode was immersed in a plating solution containing 50 g / l and glycine at 20 g / l at 50 ° C., and a current of 0.2 A / dm ² was passed for 3 minutes to form a black electrodeposited layer having a thickness of 1 μm. Thereafter, the film was dried at 60 ° C. for 30 minutes, and after cooling, a film was laminated thereon to obtain a light-transmitting electromagnetic wave shielding material having an electroplated film having a black color tone.

The light-transmitting electromagnetic wave shielding material thus obtained had excellent visibility and a high shielding effect.

Example 9 A metal layer of a polyester film having a thickness of 100 μm to which a copper foil having a thickness of 35 μm was bonded was patterned by photolithography into a lattice shape having a line width of 10 μm and a mesh size of 100 μm × 100 μm. Next, a printing resist MA83 is formed on this metal layer in a strip shape with a width of 10 mm from the four edges of the film.
0 (manufactured by Taiyo Ink) by screen printing,
After drying at 70 ° C. for 30 minutes, a mask layer was formed. A conductive wire was connected to this, immersed in a plating solution at 55 ° C. containing 70 g / l of nickel sulfate, 40 g / l of nickel ammonium sulfate, 20 g / l of zinc sulfate, and 20 g / l of sodium thiocyanate, and 1 A / dm ² Was applied for 3 minutes to form a black electrodeposited layer. Next, the mask layer was dissolved and removed with butyl cellosolve to obtain a translucent electromagnetic wave shielding material having a grounded portion where the metal layer was exposed at the end and having an electroplated film having a black color tone.

The translucent electromagnetic wave shielding material thus obtained was excellent in visibility and high in the shielding effect.

[0061]

The light-transmitting electromagnetic wave shielding material and the method of manufacturing the same according to the present invention have the above-described structure, and therefore have the following effects.

That is, since the metal layer is laminated in a pattern on the transparent substrate, there is no restriction on the line width and the pitch according to the standard, and a design that is optimal in terms of visibility and electromagnetic wave shielding effect can be freely performed. Therefore, the visibility of the translucent electromagnetic wave shielding material and the electromagnetic wave shielding effect are improved.

Further, since a black electrodeposition layer having the same register as that of the metal layer is laminated on the metal layer, no metallic luster is produced.
Therefore, the visibility of the translucent electromagnetic wave shielding material is improved. Further, since the metal layers are laminated in a pattern, visibility can be obtained without making the conductive material transparent. Therefore, there is no need to limit the material to a transparent conductive material, and a material having high conductivity can be selected from a wider range of materials, and the electromagnetic wave shielding effect is improved.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one embodiment of a manufacturing process of a translucent electromagnetic wave shielding material of the present invention.

FIG. 2 is a schematic view showing one example of a pattern of a black electrodeposition layer.

FIG. 3 is a schematic view showing an example of a pattern of a black electrodeposition layer.

FIG. 4 is a schematic view showing an example of a pattern of a black electrodeposition layer.

FIG. 5 is a schematic view showing one example of a pattern of a black electrodeposition layer.

FIG. 6 is a schematic view showing an apparatus for depositing a black electrodeposition layer on a metal layer according to the present invention.

FIG. 7 is a schematic view showing one embodiment of a translucent electromagnetic wave shielding material having a ground portion.

FIG. 8 is a schematic view showing one embodiment of a manufacturing process of the translucent electromagnetic wave shielding material of the present invention.

FIG. 9 is a schematic view showing an apparatus for depositing a black electrodeposition layer on a metal layer according to the present invention.

FIG. 10 is a schematic view showing one embodiment of a manufacturing process of the translucent electromagnetic wave shielding material of the present invention.

FIG. 11 is a schematic view showing an apparatus for depositing a black electrodeposition layer on a metal layer according to the present invention.

FIG. 12 is a schematic view showing one embodiment of a manufacturing process of the translucent electromagnetic wave shielding material of the present invention.

FIG. 13 is a schematic view showing an apparatus for depositing a black electrodeposition layer on a metal layer according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent base 2 Metal layer 3 Black electrodeposition layer 4 Counter electrode 5 Grounding part 6 Transparent electromagnetic wave shielding part 7 Mask layer 8 Positive resist layer

Claims (21)

[Claims] 1. A light-transmitting electromagnetic wave shielding material comprising: a metal layer laminated on a transparent substrate in a pattern; and a black electrodeposition layer aligned with the metal layer laminated on the metal layer. 2. A light-transmitting material, wherein a metal layer is laminated in a pattern on a transparent substrate, and a black electrodeposition layer which coincides with the metal layer except for a ground portion is laminated on the metal layer. Electromagnetic wave shielding material. 3. The light-transmitting electromagnetic wave shielding material according to claim 1, wherein the black electrodeposition layer contains black particles in the ionic polymer. 4. The method according to claim 3, wherein the ionic polymer is obtained by aminating or carboxylating an acrylic resin, a polyester resin, a polybutadiene resin, a maleic resin, an epoxy resin, a urethane resin, a polyamide resin or a modified product thereof. Transparent electromagnetic wave shielding material. 5. The translucent electromagnetic wave shielding material according to claim 3, wherein the black particles are carbon black, titanium black, and aniline black. 6. The translucent electromagnetic wave shielding material according to claim 1, wherein the black electrodeposition layer is made of a black conductive polymer. 7. The conductive polymer is pyrrole, aniline,
The translucent electromagnetic wave shielding material according to claim 6, which is a polymer of thiophene and a derivative thereof. 8. The translucent electromagnetic wave shielding material according to claim 1, wherein the black electrodeposition layer is an electroplated film having a black color tone. 9. The electroplated coating having a black color tone is a nickel, chromium, rhodium, tin-nickel-copper ternary alloy or tin-nickel-molybdenum ternary alloy. Transparent electromagnetic wave shielding material. 10. A step of laminating a metal layer in a pattern on a transparent substrate, and immersing the transparent substrate having the metal layer laminated in the previous step together with a counter electrode in a solution of an ionic polymer containing black particles. A method for producing a light-transmitting electromagnetic wave shielding material, comprising a step of laminating a black electrodeposition layer on a metal layer by applying a current. 11. A step of laminating a metal layer in a pattern on a transparent substrate, a step of laminating a mask layer on a part of the metal layer, and a step of preliminarily immersing in a solution of an ionic polymer containing black particles. A step of laminating a black electrodeposited layer on the metal layer by immersing the transparent substrate on which the metal layer and the mask layer are laminated together with the counter electrode and passing an electric current, removing the mask layer and leaving the exposed portion of the metal layer a ground part. A method for producing a light-transmitting electromagnetic wave shielding material, comprising the steps of: 12. A step of laminating a metal layer in a pattern on a transparent substrate, and immersing the transparent substrate having the metal layer laminated in the previous step together with a counter electrode in a solution of an ionic polymer containing black particles. A step of laminating a black electrodeposition layer on the metal layer by applying a current, and a step of removing a part of the black electrodeposition layer to make an exposed part of the metal layer a ground part. Manufacturing method of electromagnetic wave shielding material. 13. A step of laminating a metal layer over the entire surface of a transparent substrate, a step of laminating a positive resist layer on the metal layer in a pattern, and removing portions of the metal layer not covered with the positive resist layer by etching. Step of removing the positive resist layer by exposing and developing while leaving a part, the transparent substrate laminated with the metal layer and the positive resist layer in the previous step in a solution of an ionic polymer containing black particles It is characterized by comprising the steps of immersing with the counter electrode and energizing to deposit a black electrodeposition layer on the metal layer, and removing the remaining positive resist layer to make the exposed part of the metal layer a ground part. A method for producing a translucent electromagnetic wave shielding material. 14. A step of laminating a metal layer in a pattern on a transparent substrate, and immersing the transparent substrate having the metal layer laminated in the previous step together with a counter electrode in a solution of a monomer of a conductive polymer together with a counter electrode, and applying a current. A step of laminating a black electrodeposition layer on a metal layer by a method for producing a light-transmitting electromagnetic wave shielding material. 15. A step of laminating a metal layer in a pattern on a transparent substrate, a step of laminating a mask layer on a part of the metal layer, and a step of laminating the metal layer and a conductive polymer monomer solution in a previous step. A step of immersing the transparent substrate on which the mask layer is laminated together with the counter electrode and energizing to deposit a black electrodeposition layer on the metal layer, and a step of removing the mask layer and setting the exposed portion of the metal layer to a ground portion. A method for producing a light-transmitting electromagnetic wave shielding material, comprising: 16. A step of laminating a metal layer in a pattern on a transparent substrate, and immersing the transparent substrate, in which the metal layer is laminated in the previous step, in a solution of a monomer of a conductive polymer together with a counter electrode, and energizing the same. A step of laminating a black electrodeposition layer on a metal layer by using the method, and a step of removing a part of the black electrodeposition layer to make an exposed part of the metal layer a ground part. Manufacturing method. 17. A step of laminating a metal layer on the entire surface of a transparent substrate, a step of laminating a positive resist layer on the metal layer in a pattern, and removing portions of the metal layer not covered by the positive resist layer by etching. A step of exposing and developing the positive resist layer by exposing and developing a part thereof, and a transparent substrate having a metal layer and a positive resist layer laminated in the previous step in a solution of a monomer of a conductive polymer together with a counter electrode. A step of laminating a black electrodeposited layer on the metal layer by immersion and energizing, and a step of removing the remaining positive resist layer to make an exposed part of the metal layer a ground part. Manufacturing method of optical electromagnetic wave shielding material. 18. A step of laminating a metal layer on a transparent substrate in a pattern, and a step of laminating a transparent substrate having a metal layer laminated in a previous step in a plating solution for forming an electroplating film having a black color tone together with a counter electrode. A method for producing a light-transmitting electromagnetic wave shielding material, comprising a step of laminating a black electrodeposition layer on a metal layer by immersing and applying a current. 19. A step of laminating a metal layer in a pattern on a transparent substrate, a step of laminating a mask layer on a part of the metal layer, and a step of forming an electroplating film having a black color tone in a plating solution. A step of laminating the black electrodeposition layer on the metal layer by immersing the transparent substrate on which the metal layer and the mask layer are laminated together with the counter electrode in the previous step and applying a current, removing the mask layer and removing the exposed portion of the metal layer. A method for producing a light-transmitting electromagnetic wave shielding material, comprising a step of forming an earth part. 20. A step of laminating a metal layer on a transparent substrate in a pattern, and a step of laminating the transparent substrate having the metal layer laminated in a preceding step in a plating solution for forming an electroplating film having a black color tone together with a counter electrode. A step of laminating a black electrodeposited layer on the metal layer by immersing and applying a current, and a step of removing a part of the black electrodeposited layer to make an exposed part of the metal layer a ground part. A method for producing a translucent electromagnetic wave shielding material. 21. A step of laminating a metal layer over the entire surface of a transparent substrate, a step of laminating a positive resist layer on the metal layer in a pattern, and removing portions of the metal layer not covered by the positive resist layer by etching. Step of removing the positive resist layer by exposing and developing while leaving a part, laminating the metal layer and the positive resist layer in the previous step in a plating solution for forming an electroplating film having a black color tone A step of laminating a black electrodeposition layer on the metal layer by immersing the transparent substrate together with the counter electrode and applying a current, and a step of removing the remaining positive resist layer to make the exposed portion of the metal layer a ground portion. A method for producing a light-transmitting electromagnetic wave shielding material, comprising: