JPH09298384A - Transmissive electromagnetic wave shield material and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transmissive electromagnetic wave shield material which exhibits a high visibility and a electromagnetic shield effect, and to provide a method for manufacturing the same. SOLUTION: A black coloring layer 2 is formed on a transparent substrate 1. Then, a metallic layer 3 is formed on the black coloring layer 2. Further, a resist layer 4 is formed in the form of a pattern and a part of the metallic layer 3 which is not covered with the resist layer 4 is eliminated by etching liquid. Then, a part of the black coloring layer 2 which is not covered with the metallic layer 3 which is etched for forming the pattern is bleached by the etching liquid.

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, which use a large amount of ICs and LSIs, easily generate electromagnetic waves, and the electromagnetic waves cause troubles such as malfunction 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,
And as a translucent electromagnetic wave shield material capable of seeing through the opposite side of the material, 1) a conductive net is sandwiched between glass or a transparent resin plate, or a conductive net is embedded in a glass or a transparent resin plate, 2) There was a glass or transparent resin plate on which a transparent conductive thin film such as gold or ITO was formed by vapor deposition or sputtering. Further, in the case of the transparent electromagnetic wave shield material of 1), in order to improve the visibility, the conductive net surface is dyed black to suppress the reflection on the net surface.

[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 transparent electromagnetic wave shielding material of 2), the gold film has a metallic luster, so that the visibility is poor and the IT
Since the O 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, the transparent electromagnetic wave shielding material of the present invention has a pattern in which a black dye layer laminated on a transparent substrate has a patterned decolorization portion and other non-decolorization portions. And a metal layer which is in register with the non-bleached portion is laminated on the black dyed layer. Also,
The black dyed layer may be composed of an acrylic resin, a polyester resin, a cellulose resin, a polyolefin resin, a polyvinyl alcohol resin, a natural polymer resin or a copolymer or a mixture thereof containing a dye.

The method for producing a translucent electromagnetic wave shielding material of the present invention comprises a step of providing a black dye layer on a transparent substrate, a step of providing a metal layer on the black dye layer, and a pattern of a resist layer on the metal layer. Step, the step of removing the metal layer of the portion not covered with the resist layer with an etching solution is sequentially performed, and the black dye layer of the portion not covered with the patterned metal layer in the etching step is decolorized with the etching solution. Configured to.

Further, the method for producing a translucent electromagnetic wave shielding material of the present invention comprises a step of providing a black dye layer on a transparent substrate, a step of providing a metal layer on the black dye layer, and a pattern of a resist layer on the metal layer. And the step of removing the metal layer of the part not covered with the resist layer with an etching solution, and then the black dye layer of the part not covered with the patterned metal layer is separated from the etching solution. It was configured to perform a step of decolorizing with a decolorizing solution.

Further, the method for producing a transparent electromagnetic wave shield material of the present invention comprises a step of providing a black dye layer on a transparent substrate, a step of providing a metal layer on the black dye layer, and a pattern of a resist layer on the metal layer. And the step of removing the metal layer of the portion not covered with the resist layer with an etching solution are sequentially performed, and then the step of removing the resist layer with a release solution is performed, which is patterned in the removal step of the resist layer. The black dye layer, which is not covered with the metal layer, was decolorized with a stripping solution.

Further, the method for producing a transparent electromagnetic wave shielding material of the present invention comprises a step of providing a black dye layer on a transparent substrate, a step of providing a metal layer on the black dye layer, and a patterned resist layer on the metal layer. And the step of removing the metal layer of the part not covered with the resist layer with an etching solution, and then the black dye layer of the part not covered with the patterned metal layer is separated from the etching solution. It was configured to perform the step of decolorizing with a decoloring solution and the step of stripping the resist layer with a stripping solution. Further, the method for producing a translucent electromagnetic wave shielding material of the present invention may be configured such that the black dye layer in a portion not covered with the patterned metal layer in the resist layer peeling step is decolorized by the peeling liquid. Good.

Further, in the above etching step, the black dye layer in the portion not covered with the patterned metal layer may be decolorized with an etching solution.

Further, the above-mentioned etching solution is constituted so that the main component is aqua regia, ferric nitrate aqueous solution, ferric chloride aqueous solution, cupric chloride aqueous solution or cerium nitrate aqueous solution.

Further, the decolorizing solution is an aqueous solution of a surfactant,
Sodium chlorite aqueous solution, sodium hypochlorite aqueous solution, hydrogen peroxide aqueous solution, sodium nitrate aqueous solution, stannous chloride aqueous solution, formaldehyde sodium sulfoxylate dihydrate aqueous solution, thiourea dioxide aqueous solution, sodium hydrosulfite aqueous solution, colorless It consisted of a clear aqueous solution of dye intermediate.

Further, the above-mentioned stripping solution is constituted so that an alkaline aqueous solution, an organic solvent or a mixed solution thereof is the main component. The alkaline aqueous solution may be composed of sodium hydroxide or potassium hydroxide. The organic solvent may be composed of acetone, cellosolve acetate solvent, cellosolve solvent, or alcohol solvent. The etching solution and / or the stripping solution may contain a decolorizing agent. The decolorizing agent is a surfactant, sodium chlorite, sodium hypochlorite,
It may be composed of hydrogen peroxide, sodium nitrate, stannous chloride, sodium formaldehyde sulfoxylate dihydrate, thiourea dioxide, sodium hydrosulfite, and a colorless and transparent dye intermediate.

[0017]

Embodiments of the present invention will be described below in more detail with reference to the drawings.

FIG. 1 is a schematic view showing an embodiment of the manufacturing process of the transparent electromagnetic wave shielding material of the present invention, FIGS. 2 to 5 are schematic views showing an embodiment of a metal layer pattern, and FIGS. It is a schematic diagram which shows the other Example of the manufacturing process of the transparent electromagnetic wave shield material of this invention. 1 is a transparent substrate, 2 is a black dyed layer, 20
Is a decolorized portion, 21 is a non-decolorized portion, 3 is a metal layer, and 4 is a resist layer.

In the manufacturing process of the transparent electromagnetic wave shielding material shown in FIG. 1, first, the black dyeing layer 2 and the metal layer 3 are sequentially provided on the transparent substrate 1 (see FIG. 1a).

The material of the transparent substrate 1 is glass, acrylic resin, polycarbonate resin, polyethylene resin, AS resin, vinyl acetate resin, polystyrene resin, polypropylene resin, polyester resin, polysulfone resin, polyether sulfone resin, polychlorinated resin. Any transparent material such as vinyl may be used. Further, the transparent substrate 1 is a plate,
There are films.

The black dyed layer 2 is a layer for suppressing the reflection on the back surface of the metal layer 3 and enhancing the visibility. The black dyeing layer 2 includes, for example, an acrylic resin, a polyester resin, a cellulose resin, a polyolefin resin, a polyvinyl alcohol resin, a natural polymer resin such as gelatin, and a copolymerized portion or mixture of these together with a black dye. It is formed by being dissolved or dispersed in a solvent and subjected to a roll coating method, a spin coating method, an entire surface printing method, or the like. Alternatively, a film made of the above resin may be formed by a roll coating method, a spin coating method, an entire surface printing method or the like, and then dyed with a black dye. Further, a heat transfer dye may be dyed on the resin film by heat transfer. Since the decoloring property of the dye from the substrate of the black dyeing layer 2 greatly differs depending on the combination of the dye and the substrate, the type of dye that can be used depends on the type of resin of the substrate. As the black dye, a commercially available one may be used, or two or more kinds of dyes having a hue other than black may be mixed and made black to be used.

As the material of the metal layer 3, for example, gold,
Use a conductive material such as silver, copper, iron, nickel, and chrome that can sufficiently shield electromagnetic waves. Also,
The metal layer 3 may not be a simple substance, but may be an alloy or a multilayer. Examples of the method of forming the metal layer 3 include a method of depositing from a vapor phase such as vapor deposition, sputtering, and ion plating, a method of bonding a metal foil, a method of electroless plating the surface of the transparent substrate 1. The thickness of the metal layer 3 is
It is preferably 0.1 μm to 50 μm. If it exceeds 50 μm, it will be difficult to finish the pattern with high accuracy.
If it is smaller than m, the minimum required conductivity for maintaining the electromagnetic wave shielding effect cannot be stably secured.

Next, a resist layer 4 is provided in a pattern on the metal layer 3 (see FIG. 1b).

The resist layer 4 is a layer used for patterning the metal layer 3 in the manufacturing process of the transparent electromagnetic wave shield material. The resist layer 4 includes photoresist, printing resist, and the like. For the photoresist, for example, a photosensitive resin such as photosensitive polyimide, polyepoxy acrylate, or novolac is solidly formed on the metal layer 3 by a roll coating method, a spin coating method, an entire surface printing method, a transfer method or the like, and a mask is used. Exposed,
It is formed by development. Also, the print resist is
For example, it is a pattern formed on the metal layer 3 by offset printing or gravure printing using a resin such as polyester. The pattern of the resist layer 4 is, for example, a lattice pattern (see FIG. 2), a honeycomb pattern (see FIG. 3), a ladder pattern (see FIG. 4), an inverted polka dot pattern (see FIG. 5), or the like.

Next, the portion of the metal layer 3 which is not covered with the resist layer 4 is removed by an etching solution (see FIG. 1c). The etching liquid is selected according to the material of the metal layer 3. For example, if the material of the metal layer 3 is gold, aqua regia is used, if silver, ferric nitrate aqueous solution, if copper, ferric chloride or cupric chloride aqueous solution, and if chromium, cerium nitrate aqueous solution is used. Good to do. In the manufacturing process of the transparent electromagnetic wave shielding material shown in FIG. 1, the portion of the black dyeing layer 2 which is not covered with the patterned metal layer 3 in this etching process is decolorized by the acid of the etching solution (FIG. 1).
c). At this time, as the dye of the black dyeing layer 2, a dye that is easily decolorized by an etching solution is selected and used.

As a result of the above steps, the black dyeing layer 2 laminated on the transparent substrate 1 is composed of the patterned decolorizing portion 20 and other non-bleaching portions 21, and the non-bleaching portion 2 is formed on the black dyeing layer 2.
A transparent electromagnetic wave shield material in which the metal layer 3 which is in register with 1 is laminated is obtained. The translucent electromagnetic wave shield material has a translucent portion where the metal layer 3 is removed and the decolorization portion 20, and the non-decolorization portion 21 of the black dyeing layer 2 which is in register with the metal layer 2 has the surface of the metal layer 3 The reflection at is suppressed.

The manufacturing process of the translucent electromagnetic wave shield material is not limited to the above-mentioned embodiment, and the resist layer 4 may be stripped by a stripping solution after the etching is completed (see FIG. 6). As the stripping solution, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, an organic solvent such as acetone or ethyl cellosolve acetate,
It is advisable to use a mixture of these.

The black dye layer 2 and the metal layer 3 are sequentially provided on the transparent substrate 1 (see FIG. 7a), and the resist layer 4 is provided on the metal layer 3 in a pattern (see FIG. 7b). The metal layer 3 on the part not covered with 4 is removed by an etching solution (see FIG. 7c), and then the black dye layer 2 on the part not covered with the patterned metal layer 3 is decolorized separately from the etching solution. The solution may be decolorized (see FIG. 7d). As the decolorizing solution, an aqueous solution of a surfactant, an aqueous solution of sodium chlorite, an aqueous solution of sodium hypochlorite, an aqueous solution of hydrogen peroxide, an aqueous solution of sodium nitrate, an aqueous solution of stannous chloride, an aqueous solution of sodium formaldehyde sulfoxylate dihydrate, and dioxide. There are a thiourea aqueous solution, a sodium hydrosulfite aqueous solution, a colorless and transparent dye intermediate aqueous solution, and the like, and a decolorizing agent suitable for the dye of the black dyeing layer 2 is appropriately used. However, as compared with the case of performing decolorization at the same time as the above-mentioned etching, an extra step only for decolorization is required,
Simultaneous decolorization by etching is preferable.

Further, as shown in FIG. 8, a black dyeing layer 2 and a metal layer 3 are sequentially provided on a transparent substrate 1 (see FIG. 8a), and a resist layer 4 is provided in a pattern on the metal layer 3 (see FIG. 8A). Figure 8b
), The metal layer 3 in the portion not covered with the resist layer 4
Is removed by an etching liquid (see FIG. 8c), the resist layer 4 is peeled off, and the black dye layer 2 in a portion not covered with the patterned metal layer 3 is peeled off by a peeling liquid in the peeling process of the resist layer 4. It may be decolorized (see Figure 8d). In this case, since decoloring is performed at the same time as peeling the resist layer, a process for decolorizing is not required, and the translucent material can be easily manufactured.

Decolorization in the manufacturing process of the transparent electromagnetic wave shield material of the present invention may be performed in a plurality of steps after the etching step.

Further, a decolorizing agent may be added to the etching solution and / or the stripping solution. By doing so, the possibility of use is expanded even for a dye that is difficult to be decolorized by the acid of the etching solution and the alkali or organic solvent of the stripping solution. Examples of the decolorizing agent include surfactants, sodium chlorite, sodium hypochlorite, peroxides such as hydrogen peroxide, sodium nitrate, stannous chloride, formaldehyde sodium sulfoxylate dihydrate, and thiodioxide. Examples include urea, sodium hydrosulfite, and colorless and transparent dye intermediates.

[0032]

【Example】

Example 1 An acrylic plate having a thickness of 2 mm was used as a transparent substrate, and an N, N-dimethylformamide solution of polyacrylonitrile was applied to one surface of the transparent substrate by a bar coater and dried, and then a black dye (Sumiacrylic Black manufactured by Sumitomo Chemical Co., Ltd.) was used. It was immersed in a dye bath of FFP) for 20 minutes to provide a black dye layer. Next, silver was vapor-deposited on the entire surface of the black staining layer to provide a metal layer. Next, using a photoresist material (OFPR800 made by Tokyo Ohka Co., Ltd.), a resist layer is formed on the entire metal layer by spin coating, exposed using a photomask, and developed to develop a grid with a line width of 20 μm and a pitch of 150 μm. Patterned. Then, the metal layer in the portion not covered with the resist layer was removed with an aqueous solution of ferric nitrate / sodium chlorite, and at the same time, the black dyed layer in the portion not covered with the metal layer was decolorized by the above etching solution.

The light-transmitting electromagnetic wave shielding materials thus obtained were all excellent in visibility and high in shielding effect.

Example 2 A cellulose acetate plate having a thickness of 1 mm was used as a transparent substrate, and one surface thereof was immersed in an n-propyl alcohol / water mixed solvent solution of an ethylene / vinyl alcohol copolymer (Eval F manufactured by Kuraray Co., Ltd.). Black dye (Lanasy manufactured by Sand Co.
nBrill Black A) was applied with an applicator and dried to form a black dyed layer. Next, after immersion in an aqueous solution of palladium chloride, electroless copper plating was performed to provide a metal layer. Next, using a photoresist material (OFPR800 manufactured by Tokyo Ohka), a resist layer was formed on the entire metal layer by spin coating, exposed using a photomask, and then developed to form a honeycomb with a width of 30 μm and a pitch of 200 μm. Patterned. Next, the ferric chloride aqueous solution was used to remove the metal layer in the portion not covered with the resist layer. Finally, the resist layer was peeled off with a 3% aqueous solution of potassium hydroxide, and at the same time, the portion of the black dyed layer not covered with the metal layer was decolorized with the above peeling solution.

The transparent electromagnetic wave shielding materials thus obtained were all excellent in visibility and high in shielding effect.

[0036]

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 limitation on the line width and the pitch according to the standard, and the optimum design in terms of visibility and electromagnetic wave shielding effect can be freely made. Therefore, the visibility of the translucent electromagnetic wave shielding material and the electromagnetic wave shielding effect are improved.

Further, since the metal layer which is in register with the non-bleached portion of the black dye layer is laminated on the black dye layer, no metallic luster appears. Therefore, the visibility of the transparent electromagnetic wave shield material is improved. Further, since the metal layers are laminated in a pattern, visibility can be obtained without making the conductive material transparent. Therefore, it is not necessary 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 has been improved.

[Brief description of 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 embodiment of a pattern of a metal layer.

FIG. 3 is a schematic view showing one embodiment of a pattern of a metal layer.

FIG. 4 is a schematic view showing one embodiment of a pattern of a metal layer.

FIG. 5 is a schematic view showing one embodiment of a pattern of a metal layer.

FIG. 6 is a schematic view showing another example of the manufacturing process of the transparent electromagnetic wave shield material of the invention.

FIG. 7 is a schematic view showing another embodiment of the manufacturing process of the transparent electromagnetic wave shielding material of the present invention.

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

[Explanation of symbols]

 1 Transparent Substrate 2 Black Dye Layer 3 Metal Layer 4 Resist Layer 20 Decolorization Part 21 Non-Decolorization Part

Claims (15)

[Claims] 1. A black dyeing layer laminated on a transparent substrate is composed of a patterned decolorizing portion and other non-bleaching portions, and a metal layer in register with the non-bleaching portion is laminated on the black dyeing layer. A translucent electromagnetic wave shielding material characterized in that 2. The black dye layer is an acrylic resin, a polyester resin, a cellulose resin, a polyolefin resin,
The translucent electromagnetic wave shielding material according to claim 1, wherein the polyvinyl alcohol resin, the natural polymer resin, or a copolymer or mixture thereof contains a dye. 3. A step of providing a black dyeing layer on a transparent substrate, a step of providing a metal layer on the black dyeing layer, a step of providing a resist layer in a pattern on the metal layer, and a metal of a portion not covered with the resist layer. Production of a translucent electromagnetic wave shield material characterized in that the steps of removing layers with an etching solution are sequentially performed, and the portion of the black dyed layer that is not covered by the patterned metal layer in the etching step is decolorized with the etching solution. Method. 4. A step of providing a black dyed layer on a transparent substrate, a step of providing a metal layer on the black dyed layer, a step of providing a resist layer in a pattern on the metal layer, and a metal of a portion not covered with the resist layer. The steps of sequentially removing the layers with an etching solution, and then performing a step of decolorizing the portion of the black dyed layer not covered with the patterned metal layer with a decolorizing solution separate from the etching solution. Manufacturing method of optical electromagnetic wave shield material. 5. A step of providing a black dyed layer on a transparent substrate, a step of providing a metal layer on the black dyed layer, a step of providing a resist layer in a pattern on the metal layer, and a metal part not covered with the resist layer. The steps of removing the layers with an etching solution are sequentially performed, followed by the step of removing the resist layer with a remover solution, and the black dyed layer that is not covered with the patterned metal layer is removed in the step of removing the resist layer. A method for producing a translucent electromagnetic wave shield material, which comprises decolorizing with a liquid. 6. A step of providing a black dye layer on a transparent substrate, a step of providing a metal layer on the black dye layer, a step of providing a resist layer in a pattern on the metal layer, and a metal of a portion not covered with the resist layer. The steps of removing the layers with an etching solution are sequentially performed, and then the step of decolorizing the black dyed layer of the portion not covered by the patterned metal layer with a decoloring solution different from the etching solution, and the resist layer with a removing solution. A method of manufacturing a light-transmitting electromagnetic wave shield material, comprising: 7. The method for producing a light-transmitting electromagnetic wave shield material according to claim 6, wherein the black dye layer in a portion which is not covered with the patterned metal layer in the resist layer peeling step is decolorized with a peeling solution. 8. The light-transmitting electromagnetic wave shield material according to claim 4, wherein the black dye layer in the portion not covered with the patterned metal layer in the etching step is decolorized with an etching solution. Production method. 9. The etching solution containing an aqua regia, ferric nitrate aqueous solution, ferric chloride aqueous solution, cupric chloride aqueous solution or cerium nitrate aqueous solution as a main component. Manufacturing method of transparent electromagnetic wave shield material. 10. The decolorizing solution is an aqueous solution of a surfactant, an aqueous solution of sodium chlorite, an aqueous solution of sodium hypochlorite, an aqueous solution of hydrogen peroxide, an aqueous solution of sodium nitrate, an aqueous solution of stannous chloride, sodium formaldehyde sulfoxylate dihydrate. The method for producing a translucent electromagnetic wave shield material according to claim 4, which is an aqueous solution, an aqueous thiourea dioxide solution, an aqueous sodium hydrosulfite solution, or an aqueous solution of a colorless and transparent dye intermediate. 11. The stripping solution contains an alkaline aqueous solution, an organic solvent, or a mixed solution thereof as a main component.
A method for producing the translucent electromagnetic wave shielding material described. 12. The alkaline aqueous solution is sodium hydroxide,
The method for producing a translucent electromagnetic wave shield material according to claim 11, which is potassium hydroxide. 13. The method for producing a translucent electromagnetic wave shield material according to claim 11, wherein the organic solvent is acetone, a cellosolve acetate solvent, a cellosolve solvent, or an alcohol solvent. 14. The method for producing a translucent electromagnetic wave shield material according to claim 3, wherein the etching solution and / or the stripping solution contains a decolorizing agent. 15. The decolorizing agent is a surfactant, sodium chlorite, sodium hypochlorite, hydrogen peroxide, sodium nitrate, stannous chloride, sodium formaldehyde sulfoxylate dihydrate, thiourea dioxide, hydrosal. The method for producing a translucent electromagnetic wave shield material according to claim 14, which comprises sodium phytoite and a colorless and transparent dye intermediate.