JP2007180113A - Frequency selective transmission type electromagnetic wave shielding material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve transparency (invisible) and productivity in a frequency selective transmission type electromagnetic wave shielding material. <P>SOLUTION: In the frequency selective transmission type electromagnetic wave shielding material 1, a metallic mesh pattern 3 is arranged at least on one face of a transparent substrate 2 with slits 5 through which an electromagnetic wave of a prescribed frequency transmits. A development silver layer 4a is generated on the transparent substrate 2 by a photography process, and a metal plating layer 4b is laminated on it. Thus, a metal layer 4 of the metallic mesh pattern 3 is constituted. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention selectively transmits electromagnetic waves of a predetermined frequency and shields electromagnetic waves of other frequencies, and is a frequency selective transmission type electromagnetic shielding material excellent in transparency (not visible) and productivity, and its manufacture Regarding the method.

  In recent years, electromagnetic waves generated from various electronic devices have a negative effect on the human body and malfunction of surrounding electronic devices has become a problem. Furthermore, with the spread of wireless LAN, communication data in buildings has been It is necessary to prevent leakage and interception outside of the device, and countermeasures against frequency selective electromagnetic shielding that selectively transmits or shields only electromagnetic waves of a predetermined frequency are becoming more and more important .

  Conventionally, a transparent conductive film (such as ITO) or a conductive metal mesh pattern is formed on a transparent substrate, and an electromagnetic shielding material with transparency that can be applied to a window glass or the like has been known. However, the frequency of the electromagnetic wave to be shielded cannot be selected. When such a completely-shielded electromagnetic shielding material with transparency is pasted on the window glass, wireless LAN communication data can be prevented from leaking, and at the same time, necessary communication radio waves such as mobile phones can be shielded simultaneously. There was an inconvenience that it would.

For this reason, in order to transmit only an electromagnetic wave having a specific frequency such as a frequency band used in a cellular phone, a conductive layer provided with a slit is used (see, for example, Patent Documents 1 and 2).
Patent Document 1 has a configuration in which a conductive layer is formed on a substrate formed of resin, glass, or the like by a method such as vapor deposition or printing, and a rectangular opening (hereinafter referred to as a slit) is formed in the conductive layer. It is shown.
Patent Document 2 discloses a film having electromagnetic wave shielding properties in which an electromagnetic wave transmitting opening having a specific pattern such as a rectangular slit is formed in a conductor layer such as a metal foil. Such a slit serves as a slot antenna that captures an electromagnetic wave that resonates at a specific frequency in accordance with the shape of the slit.

On the other hand, as a method for producing an electromagnetic wave shielding material using a conductive metal mesh, photographic silver-plated is formed by developing metal silver by a photographic process to form a fine line pattern and then plating on this metal silver. There are laws (for example, Patent Documents 3 and 4).
There are two methods shown in the following (a) and (b) for forming a metallic silver mesh pattern by a photographic process.

(A) A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver part and a light-transmitting part, and the metallic silver part is further subjected to physical development and A method of forming a conductive metal part in which conductive metal particles are supported on the metal silver part by plating (see, for example, Patent Document 3). In this method, developed silver does not appear in the portion that is covered with the exposure mask and is not exposed, and developed silver appears in the portion that is not covered with the exposure mask and exposed. Therefore, compared with the exposure mask. This is a negative exposure / development method in which developed silver appears in an inverted form.

(B) A light-sensitive material having a physical development nucleus layer and a silver halide emulsion layer in this order is exposed on a transparent substrate, and metallic silver is deposited on the physical development nucleus in an arbitrary fine line pattern. A method of plating a metal using the physically developed metallic silver as a catalyst nucleus after removing a layer provided on the development nucleus (see, for example, Patent Document 4). In this method, developed silver appears in a portion which is covered with the exposure mask and is not exposed, and developed silver does not appear in a portion which is not covered with the exposure mask and exposed. Is a positive exposure / development method (silver complex diffusion transfer method, hereinafter referred to as DTR method).
JP 2002-033592 A JP 2003-124673 A JP 2004-221564 A International Publication No. 2004/007810 Pamphlet

In Patent Document 1, a conductive layer is formed on a substrate made of resin, glass or the like by a method such as vapor deposition or printing, a predetermined slit is formed in the conductive layer, and the electromagnetic wave is attached to an indoor wall or the like. Although it is disclosed that a blocking structure (frequency selective transmission type electromagnetic shielding material) is obtained, there is no description about a specific method of forming a slit.
In addition, when a slit is formed after forming a conductive layer on the entire surface of the substrate by a method such as vapor deposition or printing, the remaining conductive layer that is not opened is opaque and has no transparency (not visible). Therefore, there has been a problem that the electromagnetic wave shielding structure (frequency selective transmission type electromagnetic wave shielding material) having a slit of Patent Document 1 cannot be used by being attached to a window glass of a building or the like.

On the other hand, in Patent Document 2, as an example, a film obtained by bonding an aluminum foil (thickness 15 μm) to a PET film (thickness 100 μm) is provided with an electromagnetic wave transmission opening of 7.5 mm × 0.6 mm on the aluminum foil, It is described that a film having electromagnetic wave shielding properties (frequency selective transmission type electromagnetic wave shielding material) is prepared, but there is no specific description about the method of forming the opening.
When a slit having a predetermined shape is formed on a metal foil, when the photolithographic etching method, which is a general technique, is used, it is a problem from the viewpoint of saving resources to dissolve and remove the metal. In addition, there is a problem that the cost of processing the waste liquid used in the etching process increases.
Further, when a slit is formed in the metal foil, the metal foil that remains without being opened is opaque and has no transparency (not visually observed). Therefore, the electromagnetic wave shielding film (frequency selective transmission type electromagnetic wave shielding material) provided with slits for electromagnetic wave transmission of Patent Document 2 cannot be used by being attached to a window glass of a building or the like. It was.

  Thus, conventionally, it has excellent transparency (not visible) suitable for being attached to a window glass of a large building, and selectively transmits only electromagnetic waves of a predetermined frequency, and electromagnetic waves of other frequencies. A frequency selective transmission type electromagnetic shielding material and a method for producing the same have not been known.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the electromagnetic wave shielding material of the frequency selective transmission type excellent in transparency (not visually observed) and productivity, and its manufacturing method.

In order to solve the above problems, the present invention is a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate. The metal layer of the metal mesh pattern is composed of a developed silver layer produced by a photographic method and a metal plating layer laminated thereon, and a frequency selective transmission type electromagnetic shielding material, I will provide a.
The metal plating layer is preferably an electroless plating layer and / or an electrolytic plating layer.
The metal layer preferably has a line width of 15 to 60 μm and a thickness of 0.5 to 15 μm.
The surface of the metal plating layer is preferably blackened.
The developed silver layer is preferably a developed silver layer produced by a positive photographic process or a developed silver layer produced by a negative photographic process.

  Further, the present invention is a method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate, By exposing and then developing a base material on which at least one surface of the transparent base material is provided with a layer containing a substance that deposits metallic silver by exposure and development, a silver mesh layer having the slit is developed. And a plating process for forming a metal plating layer on the developed silver layer. The method for producing a frequency selective transmission type electromagnetic wave shielding material is provided.

  Further, the present invention is a method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate, By exposing a base material provided with a layer containing a substance capable of depositing metallic silver by exposure and development to at least one surface of a long transparent base material using a continuous exposure apparatus, and then developing, A step of producing an original roll in which a metal mesh pattern having a slit is generated by a developed silver layer, and after continuously feeding the transparent substrate provided with the developed silver layer from the original roll, electroless plating and And / or a plating step in which a metal plating layer is formed on the developed silver layer by electrolytic plating and is wound again to form a roll body. To provide a process for the preparation of the 4-option transparent electromagnetic wave shielding material.

  Further, the present invention is a method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate, A substrate having a layer containing a substance that deposits metallic silver by exposure and development is continuously drawn on at least one surface of the long transparent substrate, and the transparent substrate is exposed using a continuous exposure apparatus. Then, by developing, a metal mesh pattern having the slit is generated by the developed silver layer, and subsequently, a metal plating layer is formed on the developed silver layer by electroless plating and / or electrolytic plating continuously. Then, a method of manufacturing a frequency selective transmission type electromagnetic wave shielding material, which is wound up again to form a roll body, is provided.

The continuous exposure apparatus includes a cylindrical drum made of a material that transmits light used for exposure, an exposure mask portion provided on an outer peripheral wall of the cylindrical drum, and an exposure light source disposed in the cylindrical drum. The apparatus which irradiates light from the inside of a cylindrical drum with respect to the transparent base material wound around the said cylindrical drum can be used.
Alternatively, as a continuous exposure apparatus, a cylindrical drum, an exposure mask film on which a continuous pattern is formed, and an exposure light source disposed outside the cylindrical drum, and transparently wound around the cylindrical drum. An apparatus for irradiating light to the base material and the exposure mask film from the outside of the cylindrical drum can also be used.

In the method for manufacturing a frequency selective transmission type electromagnetic wave shielding material of the present invention, the metal plating layer is preferably formed by copper plating and / or nickel plating.
The developed silver layer is preferably produced by a positive photographic process or a negative photographic process.

  According to the frequency selective transmission type electromagnetic shielding material of the present invention, a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is formed by laminating a metal plating layer on a developed silver layer generated by a photographic method. Therefore, the line width of the metal layer can be made sufficiently thin, and the transparency (not visually observed) and the productivity are excellent.

  According to the method of manufacturing a frequency selective transmission type electromagnetic shielding material of the present invention, a metal mesh pattern having a slit for transmitting an electromagnetic wave having a predetermined frequency is formed on a developed silver layer formed by a photographic process. Since the line width of the metal layer can be made sufficiently thin, the slit can be accurately formed at the stage of developing the developed silver layer, and transparency (not visually observed) and productivity are achieved. Excellent.

The present invention will be described below with reference to the drawings based on the best mode.
FIG. 1 is a drawing showing an example of a frequency selective transmission type electromagnetic shielding material of the present invention. FIG. 1 (a) is a front view showing a schematic configuration of the frequency selective transmission type electromagnetic shielding material, and FIG. 1 (b). Is a partially enlarged front view of the metal mesh pattern, and FIG. 1C is a partially enlarged sectional view of the metal layer constituting the metal mesh pattern. FIG. 2 is a front view showing a second example of the frequency selective transmission type electromagnetic shielding material of the present invention.
FIG. 3 is a schematic view showing an example of an apparatus for continuously performing electroless plating following exposure / development in a roll-to-roll manner. FIG. 4 is a schematic view showing an example of an apparatus for continuously performing electroless plating and electrolytic plating following exposure / development in a roll-to-roll manner.
FIG. 5 is a schematic view showing an example of an apparatus for performing electroless plating by roll-to-roll. FIG. 6 is a schematic view showing an example of an apparatus for performing electroplating by roll-to-roll. FIG. 7 is a schematic view showing an example of a continuous exposure apparatus. FIG. 8 is a schematic view showing another example of the continuous exposure apparatus.

A frequency selective transmission type electromagnetic shielding material 1 shown in FIG. 1 is provided with a metal mesh pattern 3 having a slit 5 for transmitting electromagnetic waves of a predetermined frequency on one side of a long transparent base material 2. A frequency selective transmission type electromagnetic shielding material that shields electromagnetic waves of other frequencies that do not transmit, and as shown in FIG. 1 (c), the metal layer 4 constituting the metal mesh pattern 3 was generated by a photographic process. It consists of developed silver layer 4a and metal plating layer 4b laminated on developed silver layer 4a.
If necessary, an adhesive layer and a release film (both not shown) for protecting the pressure-sensitive adhesive layer can be provided on the other surface (back surface) of the transparent substrate 2. The electromagnetic wave shielding material provided with the pressure-sensitive adhesive layer can be easily attached to the surface of glass or the like by peeling off the release film.

(Transparent substrate)
The transparent substrate 2 used in the present invention preferably has transparency in the visible region and generally has a total light transmittance of 90% or more. Especially, the resin film which has flexibility is preferable as the transparent base material 2 since it is excellent in handleability. Specific examples of the resin film used for the transparent substrate 2 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, and diacetates. A single-layer film having a thickness of 50 to 300 μm made of resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, or the like. And a multi-layer composite film.

(Metal mesh pattern 3)
The metal mesh pattern 3 disposed on the transparent substrate 2 and covering the periphery of the slit 5 is constituted by a metal mesh pattern 3 made of fine lines in order to ensure transparency (not visually observed). Here, the mesh pattern composed of fine lines (thin line mesh pattern) is not particularly limited as long as it is a pattern that becomes a mesh. For example, the mesh pattern is a net or a grid, and the transparent substrate 2 is exposed in the mesh or grid eye portion 3a. Thus, it becomes a light transmitting portion, and the electromagnetic shielding material as a whole has transparency. As the mesh pattern, for example, a pattern in which fine lines are provided in a grid shape in the vertical and horizontal directions and square eyes can be used. Other examples include triangles, hexagons, rhombuses, rectangles, circles, ellipses, and combinations thereof, and are not particularly limited.

The line width of the metal layer constituting the fine line mesh pattern is preferably 15 to 60 μm, and more preferably 15 to 30 μm. The thickness of the metal layer can be arbitrarily changed depending on desired properties, but is preferably in the range of 0.5 to 15 μm, more preferably in the range of 2 to 12 μm.
In order to improve the total light transmittance of the metal mesh, it is necessary to sufficiently increase the area of the light transmission portion between the fine lines with respect to the area of the region where the fine lines are provided. For this reason, it is preferable that the space | interval of a thin wire | line is 100-900 micrometers, More preferably, it is 150-700 micrometers. The total light transmittance of the frequency selective transmission type electromagnetic shielding material of the present invention is preferably 50% or more as an average of the total of the fine line portion and the interval between the fine lines.

  The method for producing the metal mesh pattern 3 in the frequency selective transmission type electromagnetic wave shielding material of the present invention will be described in detail later, but after generating the developed silver layer 4a in the same pattern as the target metal mesh pattern 3 by a photographic method, On the developed silver layer 4a, the metal plating layer 4b is preferably formed by electroless plating.

Although it does not specifically limit as a shape of the slit 5, You may employ | adopt shapes, such as a rectangle, a double rectangle, a double circle, a double triangle (illustration omitted). Further, a cross shape, an X shape, an inverted Y shape, a V shape, or the like (not shown) may be employed. If a complicated slit shape other than a rectangle is used, electromagnetic waves of various polarization planes can be transmitted.
In the case of the rectangular slit shown in FIG. 1, a rectangular slit having a length of about ¼ of the wavelength of the electromagnetic wave to be transmitted (passed) is preferable. The width of the slit 5 is preferably about 5% or less of the length of the slit 5. FIG. 1 illustrates the case where the length direction of the slit 5 (vertical direction in FIG. 1A) is orthogonal to the length direction of the transparent substrate 2 (horizontal direction in FIG. 1A). This arrangement is not particularly limited to this arrangement, and the slit 5 may be arranged such that the length direction of the slit 5 is parallel to the length direction of the transparent substrate 2. Further, two or more types of slits having different dimensions and / or length directions can be mixed and arranged.

  In the case of an application covering a relatively small area, the metal mesh pattern 3 of the frequency selective transmission type electromagnetic shielding material 1 is shown in FIG. 2 so that the electromagnetic shielding material can be easily cut for each fixed length. A portion 6 where the metal mesh pattern 3 is cut off may be provided for each predetermined length in the length direction of the transparent substrate 2, and the metal mesh pattern 3 having the slits 5 may be separated. Thereby, it becomes easy to cut the transparent substrate 2 without cutting the metal mesh pattern 3.

  Further, in the case of an application covering a large area, the metal mesh pattern 3 of the frequency selective transmission type electromagnetic shielding material 1 is continuously continuous in the length direction of the transparent substrate 2 as shown in FIG. Provide. Thereby, there is no leakage of the electromagnetic wave from the cut | interruption 6, and the electromagnetic wave shielding effect can be acquired over the whole length direction of the electromagnetic wave shielding material 1. FIG.

(Generation of developed silver layer)
In the exposure development method based on the photographic method for producing the developed silver layer 4a, as described above, (a) developed silver appears in the exposed portion that is not covered with the exposure mask, that is, the exposure mask and The so-called negative exposure development method in which developed silver appears in the opposite form, and (b) developed silver appears in the unexposed portions covered by the exposure mask, that is, developed silver is in the same shape as the exposure mask. There are two types of so-called positive exposure and development methods. Either (a) a negative exposure / development method or (b) a positive exposure / development method can be applied to the present invention.

  Hereinafter, a method for producing a metal mesh pattern using a positive exposure / development method (DTR method) and an electrolytic plating method will be described. In the case of the DTR method, it is preferable that a physical development nucleus layer is provided in advance on the surface of the transparent substrate 2. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. These fine particle layers of physical development nuclei can be provided on the transparent substrate 2 by vacuum deposition, cathode sputtering, coating, or the like. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per square meter in solid content.

  The transparent substrate 2 can be provided with an adhesive layer of a polymer latex layer such as vinylidene chloride or polyurethane, and an intermediate layer made of a hydrophilic binder such as gelatin is provided between the adhesive layer and the physical development nucleus layer. You can also

  The physical development nucleus layer preferably contains a hydrophilic binder. The amount of the hydrophilic binder is preferably about 10 to 300% by mass with respect to the physical development nucleus. As the hydrophilic binder, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. The physical development nucleus layer may also contain a hydrophilic binder crosslinking agent.

  The physical development nucleus layer and the intermediate layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like. In the present invention, the physical development nucleus layer is preferably provided as a continuous and uniform layer by the above-described coating method.

  The supply of silver halide for precipitating metallic silver on the physical development nucleus layer is performed by a method in which the physical development nucleus layer and the silver halide emulsion layer are integrally provided in this order on the substrate, or another paper or plastic resin film. There is a method of supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate such as the above. From the viewpoint of cost and production efficiency, the former physical development nucleus layer and the silver halide emulsion layer are preferably provided integrally.

The silver halide emulsion can be produced according to a general method for producing a silver halide emulsion of a silver halide photographic light-sensitive material. The silver halide emulsion is usually prepared by mixing and ripening an aqueous silver nitrate solution, an aqueous halogen solution of sodium chloride or sodium bromide in the presence of gelatin.
The silver halide composition of the silver halide emulsion layer preferably contains 80 mol% or more of silver chloride, and more preferably 90 mol% or more is silver chloride. The conductivity of the physically developed silver formed by increasing the silver chloride content is improved.

  The silver halide emulsion layer is sensitive to various light sources. In the present invention, when forming a metal mesh pattern having a slit with physically developed silver, as a method for exposing the silver halide emulsion layer, a method of exposing the metal mesh pattern transmission original and the silver halide emulsion layer in close contact, or There are scanning exposure methods using various laser beams. The former contact exposure is possible even if the silver halide has relatively low photosensitivity, but in the case of scanning exposure using laser light, relatively high photosensitivity is required. Therefore, when the latter exposure method is used, the silver halide may be subjected to chemical sensitization or spectral sensitization with a sensitizing dye in order to increase the sensitivity of the silver halide. Chemical sensitization includes metal sensitization using a gold compound or silver compound, sulfur sensitization using a sulfur compound, or a combination thereof. Gold-sulfur sensitization using a gold compound and a sulfur compound in combination is preferable. In the above-described method of exposing with laser light, a laser beam having an oscillation wavelength of 450 nm or less, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm is used. It can be handled even under a yellow fluorescent lamp.

  Any position on the substrate on which the physical development nucleus layer is provided, for example, an adhesive layer, an intermediate layer, a physical development nucleus layer or a silver halide emulsion layer, a protective layer, or a backing layer provided with a support interposed therebetween. A dye or pigment for preventing irradiation may be contained.

  When producing developed silver using a photosensitive material in which a silver halide emulsion layer is coated directly on the physical development nucleus layer or via an intermediate layer, the transparent original with a metal mesh pattern and the photosensitive material are in close contact with each other. After exposure, or after scanning exposure of the above-mentioned photosensitive material to a digital image of a metal mesh pattern with various laser light output machines, it is processed by treatment in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. Complex salt diffusion transfer development (DTR development) occurs, the silver halide in the unexposed area is dissolved to form a silver complex salt, which is reduced on the physical development nuclei to deposit metal silver to obtain a physically developed silver thin film having a metal mesh pattern be able to. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After the development, the silver halide emulsion layer and the intermediate layer, or the protective layer provided if necessary, are removed by washing with water, and a physically developed silver thin film having a metal mesh pattern is exposed on the surface.

  After DTR development, the silver halide emulsion layer or the like provided on the physical development nucleus layer may be removed by washing with water or transferring and peeling to a release paper or the like. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like.

  On the other hand, when supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate different from the substrate on which the physical development nucleus layer was coated, the silver halide emulsion layer was exposed in the same manner as described above. After that, the substrate coated with the physical development nucleus layer and another photosensitive material coated with the silver halide emulsion layer are superposed and adhered in an alkaline solution in the presence of a soluble silver complexing agent and a reducing agent. Then, after taking out from the alkaline solution, after several tens of seconds to several minutes have passed, the both are removed to obtain a physically developed silver thin film having a metal mesh pattern deposited on the physical development nuclei.

  Next, a soluble silver complex salt forming agent, a reducing agent, and an alkali solution necessary for silver complex diffusion transfer development will be described. The soluble silver complex salt forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound that reduces this soluble silver complex salt to precipitate metallic silver on physical development nuclei. These actions are performed in an alkaline solution.

  Examples of the soluble silver complex forming agent used in the present invention include sodium thiosulfate, thiosulfate such as ammonium thiosulfate, thiocyanate such as sodium thiocyanate and ammonium thiocyanate, alkanolamine, sodium sulfite, and potassium bisulfite. Sulfites such as T. H. Examples include the compounds described in 474-475 (1977) of James The Theory of the Photographic Process 4th edition.

  As the reducing agent, a developing agent known in the field of photographic development can be used. For example, hydroquinone, catechol, pyrogallol, methylhydroquinone, polyhydroxybenzenes such as chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl- Examples include 3-pyrazolidones such as 4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like.

  The above-described soluble silver complex salt forming agent and reducing agent may be applied to the substrate together with the physical development nucleus layer, added to the silver halide emulsion layer, or contained in an alkaline solution. Further, it may be contained in a plurality of positions, but it is preferably contained in at least the alkaline liquid.

  The content of the soluble silver complex salt forming agent in the alkaline solution is suitably used in the range of 0.1 to 5 mol per liter of the developer, and the reducing agent is 0.05 to 1 per liter of the developer. It is suitable to use in the molar range.

  The pH of the alkaline solution is preferably 10 or more, and more preferably in the range of 11-14. Application of the alkaline solution for silver complex diffusion transfer development may be an immersion method or a coating method. The immersion method is, for example, a method in which a substrate provided with a physical development nucleus layer and a silver halide emulsion layer is transported while being immersed in an alkaline liquid stored in a large amount in a tank. About 40 to 120 ml of alkali solution per square meter is applied on the silver halide emulsion layer.

As described above, in the frequency selective transmission type electromagnetic shielding material of the present invention, when the line width of the fine line pattern is reduced and the interval of the grating is increased, the translucency is increased, but the conductivity (and the electromagnetic wave other than the wavelength to be transmitted is increased). On the contrary, when the line width is increased and the lattice spacing is reduced, the translucency is lowered and the conductivity is increased.
The developed silver layer formed by physical development of an arbitrary fine line pattern formed on the transparent substrate according to the present invention has a translucency with a total light transmittance of 50% or more and a conductivity with a surface resistivity of 10 ohms / □ or less. It is difficult to satisfy at the same time. Specifically, the developed silver layer by physical development has a conductivity of a surface resistivity of 50 ohms / square or less, preferably 20 ohms / square or less, but a pattern with a fine line width of 60 μm or less, for example, a fine line width of 20 μm. When the total light transmittance is 50% or more, the surface resistivity becomes several hundred ohms / square to 1000 ohms / square or more. However, the developed silver layer itself by this physical development, the metal silver particles forming the developed silver layer obtained after the development process is very small, and the amount of the hydrophilic binder present in the developed silver layer is extremely small, Since the developed silver layer is formed in a state close to the close-packed state of the metallic silver particles forming the developed silver layer and has electrical conductivity, by applying a plating (plating) with a metal such as copper or nickel, When the thin line pattern has a thickness of 0.5 to 15 μm and a line width of 15 to 60 μm, even if it is a light-transmitting thin line pattern with a total light transmittance of 50% or more, preferably 60% or more, the surface resistivity is 10 Conductivity of ohm / square or less, preferably 7 ohm / square or less can be maintained.
According to the present invention, the conductivity of the metal layer composed of the developed silver layer and the metal plating layer is high. Sexuality can be increased.

(Metal plating layer)
The plating method used when laminating the metal plating layer 4b on the developed silver layer 4a having the mesh pattern having the slits 5 can be any of an electroless plating method, an electrolytic plating method, or a plating method in which both are combined. . Since the developed silver layer 4a is conductive, an electrolytic plating method is possible. Depending on the arrangement state of the slits, the distribution of the electrolysis current becomes non-uniform and “plating unevenness” is likely to occur, and as a result, there may be a partial variation in electromagnetic shielding performance. In such a case, the electroless plating method is preferable to the electrolytic plating method. An initial plating layer may be formed by electroless plating first, and then a plating layer formed by electrolytic plating may be laminated thereon.

  In the present invention, the metal plating method can be performed by a known method, but the known electroless copper plating or electroless nickel plating is preferably used as the electroless plating method. In addition, as the electrolytic plating method, conventionally known methods such as copper, nickel, silver, gold, solder, or a copper / nickel multilayer or composite system can be used, and these are described in “Surface Treatment Technology Overview; Reference can be made to Document Center, December 21, 1987, first edition, pages 281-242.

Copper (Cu) and / or nickel (Ni) is preferable as the metal used for plating because it is easy to plate and the plating layer has excellent conductivity, can be plated into a thick film, and is low in cost. . The metal plating layer is preferably formed by laminating a plurality of layers of the same kind of metal or different kinds of metals by performing plating a plurality of times. For example, when a first plating layer is laminated on a developed silver layer and a second plating layer is further laminated thereon, one plating layer is an electroless nickel plating layer, and the other plating layer is an electroless copper. A combination that is a plating layer is preferred.
The type of plating tank used for plating may be either a vertical type or a horizontal type, but the length is determined so as to ensure a predetermined plating residence time.

(Blackening treatment)
In the present invention, a blackening layer for reducing the reflectance may be formed by applying a blackening treatment to the surface of the metal plating layer. The blackened layer may be a dark layer that hardly reflects light, and may be not only black but also blackish brown or blackish green, for example. The formation of the blackened layer is preferable because the fine metal wires are less noticeable, and for example, when an electromagnetic wave shielding material is attached to a window glass or the like, the other side can be easily seen through the transparent base material.
The blackening layer may be formed by an ink treatment by applying black ink, a blackening plating treatment by plating a metal such as ruthenium, nickel, or tin that has a black surface, or a chemical conversion treatment (oxidation treatment, etc.) of a fine metal wire. it can. Of these, in the chemical conversion treatment, a thin film of metal oxide is formed on the surface of the metal layer, so that it becomes black.

(Manufacturing equipment for continuous production)
As described above, the metal mesh pattern 3 is seamlessly formed on the long base 11 (particularly, the long base extended from the roll) in order to manufacture a frequency selective transmission type electromagnetic shielding material covering a large area. In the case of continuous production, the long base material 11 is fed out from the raw roll, and the exposure / development process of the developed silver layer and / or the plating process of the metal plating layer is carried out by a roll-to-roll. There are advantages such as improvement, which is preferable.

  In the apparatus 10 shown in FIG. 3, the raw roll 12 is a roll of a sheet in which a layer (in detail above) containing a substance that deposits metallic silver by exposure and development is provided on a long substrate 11. It is a thing. The base material 11 fed out from the raw fabric roll 12 is transferred from left to right in the figure by transfer rolls 13, 13, 13,. The substrate 11 is first transferred to the continuous exposure device 14 and baked (exposed) with a predetermined mask pattern. Here, the continuous exposure device 14 is a device that performs exposure while transferring the transparent base material by continuous feeding, as will be described in detail later.

  Next, the exposed base material 11 is transferred to the developing device 15, and the developed silver that has been photographic developed is fixed in a mesh pattern shape. Next, after passing through the water washing tank 16 and being cleaned, unnecessary foreign matters and contaminants are removed, it is transferred to the electroless plating tank 17 for performing a plating process.

In the electroless plating tank 17, electroless plating is performed through an electroless plating solution 18, and an electroless plating layer is deposited on the developed silver layer on the surface of the substrate 11. The temperature of the electroless plating solution 18 is controlled by a temperature regulator (not shown) so as to be a predetermined temperature. The electroless plating solution 18 can leak and fall from a gap (slit) through which the substrate 11 of the electroless plating tank 17 is passed. Therefore, a receiving tank 19 that receives the leaked electroless plating solution 18 is installed below the electroless plating tank 17, and the electroless plating solution 18 received in the receiving tank 19 is supplied to the circulation pump 20 and the filter 21. Then, it is configured to be recirculated to the electroless plating tank 17 again.
The substrate 11 that has exited the electroless plating tank 17 is washed away with unnecessary electroless plating solution 18 in a water washing tank 22, drained and dried by a drier 23, and is wound around a roll 24 again.

  Further, in the plating process, a plurality of sets (two or more sets) of the electroless plating tank 17 and the water washing tank 22 are repeatedly installed, and the electroless plating is performed a plurality of times during one roll-to-roll process. It is also possible to obtain a metal mesh pattern comprising a developed silver layer and a metal layer on which two or more metal plating layers are laminated.

  According to the apparatus configuration shown in FIG. 3, during one roll-to-roll process, the development of a developed silver layer (exposure / development process) and the formation of an electroless metal plating layer (metal plating process) are performed by a photographic method. The process can be carried out continuously, and the processing speed can be further improved and the cost can be reduced. In this embodiment, it is preferable to perform a metal plating step after the development silver layer is produced by the photographic manufacturing method, while the surface of the substrate is kept wet. In this case, it is possible to reduce the occurrence of plating defects due to microbubbles adhering to the surface of the developed silver layer and hindering contact with the plating solution.

Similarly, according to the apparatus configuration shown in FIG. 4, during one roll-to-roll process, a developed silver layer is formed by a photographic method (exposure / development process) and an electroless metal plating layer is formed (metal). The plating step) and the formation of the electrolytic metal plating layer (metal plating step) can be carried out continuously, so that the processing speed can be further improved and the cost can be reduced.
A manufacturing apparatus 10A shown in FIG. 4 is an apparatus that performs electrolytic plating after electroless plating. In this manufacturing apparatus 10A, since the structure from the raw fabric roll 12 to the electroless plating tank 17 is the same as that of the manufacturing apparatus 10 shown in FIG. Note that the alternate long and short dash line in FIG. 4 indicates that the left side and the right side of the apparatus are divided into two upper and lower stages due to dimensional limitations in the drawing, and the base material 11 has an upper solid line portion at the right end and a lower stage. Please understand that it is directly connected to the left end of the solid line.
The base material 11 exiting the electroless plating tank 17 is transferred to the electrolytic plating tank 25 after washing away unnecessary electroless plating solution 18 in the water washing tank 22.

  In the electrolytic plating tank 25, electrolytic plating is performed between the feed rolls 26, 26 serving as the cathode and the positive electrode plates 27, 27 serving as the anode through the electrolytic plating solution 28, and formed on the developed silver mesh pattern of the substrate 11. An electrolytic plating layer is deposited on the electroless plating layer. The temperature of the electrolytic plating solution 28 is controlled by a temperature regulator (not shown) so as to be a predetermined temperature. The power supply rolls 26 and 26 are provided at the entrance / exit for the base material 11 to enter and exit the electrolytic plating tank 25, and the electrolytic plating solution 28 leaks from the gap between the power supply rolls 26 and 26 of the electrolytic plating tank 25. Can fall. Therefore, a receiving tank 19 that receives the leaked electrolytic plating solution 28 is installed below the electrolytic plating tank 25, and the electrolytic plating solution 28 received by the receiving tank 19 passes through the circulation pump 20 and the filter 21 again. It is configured to recirculate to the electrolytic plating tank 47.

  The base material 11 exiting the electrolytic plating tank 25 is washed away with unnecessary electrolytic plating solution 28 in the water washing tank 22, drained and dried by the dryer 23, and wound around the roll 24 again.

Further, the manufacturing apparatus 10B shown in FIG. 5 is formed from an original roll 12A on which at least one surface of a long base 11 is exposed and developed by a photographic method and developed silver is fixed in the shape of a metal mesh pattern. It is an apparatus that feeds the substrate 11 and performs electroless plating continuously. In the manufacturing apparatus 10B shown in FIG. 5, the base material 11 is transferred from the raw roll 12 </ b> A wound in a roll shape to the right to the left in the drawing by the transfer rolls 13, 13, 13,. It is transferred to. The base material 11 is first passed through the water cleaning tank 16 and cleaned to remove unnecessary foreign matters and contaminants. Next, it transfers to the electroless-plating tank 17 in order to perform a plating process.
In the manufacturing apparatus 10B of FIG. 5, the configuration from the electroless plating tank 17 to the product roll 24 is the same as that of the manufacturing apparatus 10 shown in FIG.

Also, the manufacturing apparatus 10C shown in FIG. 6 is provided with an original fabric roll 12A in which at least one surface of the long base 11 is exposed and developed by a photographic method and developed silver is fixed in the shape of a metal mesh pattern. It is an apparatus that feeds out the substrate 11 and performs electrolytic plating continuously. In the manufacturing apparatus 10C shown in FIG. 6, the base material 11 is transferred from the left side to the right side of the figure by the transfer rolls 13, 13, 13,. It is transferred to. The base material 11 is first passed through the water cleaning tank 16 and cleaned to remove unnecessary foreign matters and contaminants. Next, it is transferred to the electrolytic plating tank 25 for performing a plating process.
In the manufacturing apparatus 10C of FIG. 6, the configuration from the electrolytic plating tank 25 to the product roll 24 is the same as that of the manufacturing apparatus 10A shown in FIG.

(Exposure equipment)
As an exposure apparatus using the above exposure method, there are a single wafer processing type exposure apparatus using a single wafer type exposure mask (photomask) and a continuous exposure apparatus capable of forming a continuous pattern. A single wafer processing type exposure apparatus uses a single wafer type exposure mask (photomask) on which a predetermined mask pattern is formed, feeds the substrate to the exposure apparatus intermittently, and evacuates the inside of the apparatus for exposure. After the mask and the substrate are brought into close contact with each other and no gap is formed, exposure is performed with, for example, ultraviolet rays. In a single wafer processing type exposure apparatus, since vacuum evacuation, exposure, and release to the atmosphere are intermittently performed, continuous production cannot be performed, and the processing speed becomes slow.

On the other hand, as illustrated in FIGS. 7 and 8, when continuous exposure apparatuses 30 and 40 capable of continuously exposing the substrate are used, the processing speed is higher than that of the single-wafer processing type exposure apparatus, and continuous. There is an advantage that efficient production becomes possible.
As shown in FIGS. 3 and 4, these continuous exposure apparatuses 30 and 40 are incorporated into the manufacturing apparatuses 10 and 10 </ b> A when the exposure / development process and the plating process are continuously performed by roll-to-roll. As the continuous exposure apparatus 14, continuous exposure apparatuses 30 and 40 exemplified in FIGS. 7 and 8 can be used. Also, as shown in FIGS. 5 and 6, when performing the exposure / development process separately from the roll-to-roll process for performing the plating process, continuous exposure and development are performed by an apparatus provided separately from the manufacturing apparatuses 10B and 10C. To produce the raw roll 12A.
In the drawings showing the continuous exposure apparatuses 30 and 40, the base material used for the exposure is the case where the manufacturing apparatuses 10 and 10A shown in FIGS. 3 and 4 are used, and the manufacturing apparatus 10B shown in FIGS. The description will be made with the common reference numerals 34 and 44 without distinguishing from the case of using 10C.

  A continuous exposure apparatus 30 shown in FIG. 7 includes a cylindrical drum 31 made of a material that transmits light used for exposure in a photographic manufacturing method, an exposure mask portion 32 provided on the outer peripheral wall of the cylindrical drum 31, and the inside of the cylindrical drum 31. And an exposure light source 33 disposed on the surface of the cylindrical drum 31, and the substrate 34 wound around the cylindrical drum 31 is exposed by light emitted from the light source 33 inside the cylindrical drum 31. In the continuous exposure apparatus 30, a light source cover 35 having an opening 36 that transmits light in a specific irradiation direction can be provided around the exposure light source 33. The pattern for exposing the substrate 34 (that is, the pattern corresponding to the metal mesh pattern) is determined by the pattern of the portion of the exposure mask portion 32 that transmits light. The exposure mask portion 32 is disposed on the cylindrical drum 31 by, for example, being provided on the surface (inner surface or outer surface) of the outer peripheral wall of the cylindrical drum 31 or being inserted or sandwiched inside the outer peripheral wall. FIG. 7 is a diagram illustrating the case where the exposure mask portion 32 is provided on the outer surface of the outer peripheral wall of the cylindrical drum 31.

  In this continuous exposure apparatus 30, the cylindrical drum 31 rotates at the same speed as the base material 34 that is continuously transferred, so that each part of the base material 34 is exposed at a place where the cylindrical drum 31 is wound. In the meantime, the pattern of the exposure mask portion 32 with respect to the base material 34 (the pattern of the light transmitting portion and the light shielding portion) is not shifted, and the exposure for the required time can be continued. The light source 33 used in the exposure apparatus can be appropriately selected depending on the spectral characteristics and sensitivity of the silver halide emulsion contained in the silver halide emulsion layer. For example, a tungsten lamp, an ultraviolet lamp, a fluorescent lamp, a xenon lamp, a metal halide A lamp or the like can be used. At the time of exposure, the light source cover 35 does not rotate, and the opening 36 always faces in a certain direction (the right direction in FIG. 7), so that the light source 33 is located in a portion where the base material 34 is away from the surface of the cylindrical drum 31. Is blocked by the light source cover 35. That is, the exposure of the base material 34 by the light source 33 of the continuous exposure apparatus 30 is performed within a certain range 37 in which the base material 34 is wound around the surface of the cylindrical drum 31 on the transfer path. By adjusting the exposure light amount and the irradiation time in accordance with the above, the optimum light amount can be reliably irradiated.

On the other hand, the continuous exposure apparatus 40 shown in FIG. 8 includes a cylindrical drum 41, an exposure mask film 42 on which a pattern corresponding to a metal mesh pattern is formed, and an exposure light source 43 disposed outside the cylindrical drum 41. The apparatus is configured to irradiate the substrate 44 wound around the cylindrical drum 41 with light from the outside of the cylindrical drum 41 and to expose the substrate 44 through the exposure mask film 42.
The exposure mask film 42 is formed by forming a pattern to be a mask on a transparent resin film by a known method such as a photolithographic method using reduced exposure. 41 is used for exposure. Thereafter, the exposure mask film 42 is cut off from the base material 44, wound up, and used repeatedly.
When the light source 43 is outside the cylindrical drum 41, the transparency of the cylindrical drum 41 is not particularly limited, and may be opaque.

  In the continuous exposure apparatus 40, a light source cover 45 having an opening 46 that transmits light in a specific irradiation direction can be provided around the light source 43 for exposure. Thereby, the exposure of the base material 44 by the light source 43 is performed within a certain range 47 in which the base material 44 is wound around the surface of the cylindrical drum 41 on the transfer path, so that the exposure light amount and the irradiation time are controlled. Can be performed reliably. Here, as the light source 43, the same light source 33 as that of the above-described continuous exposure apparatus 30 can be used.

Since the continuous exposure apparatus 40 shown in FIG. 8 continuously transfers the superposed base material 44 and the exposure mask film 42 while being wound around the cylindrical drum 41, it can be transferred while applying an appropriate tension to both. The transfer speed is easy to control, and the pattern of the exposure mask film 42 on the substrate 44 (light-transmitting portion and light-shielding portion) is exposed while the portions of the substrate 44 are exposed at the portions wound around the cylindrical drum 41. Therefore, the exposure for the required time can be continued.
In addition to the continuous exposure apparatuses 30 and 40 exemplified above, for example, the superimposed transparent base material and exposure mask film are continuously exposed using a light source while being continuously conveyed along a linear path. An apparatus or the like can also be used. Further, the number of light sources for exposure is not particularly limited, and a plurality (in a plurality of locations) may be provided as necessary.

  According to the present invention, a frequency selective transmission type electromagnetic wave shield that is supplied by a wide sheet (particularly in a continuous roll sheet state) for covering a large area such as a window glass of a large building that cannot be handled by a conventional manufacturing method. Since the material can be manufactured, it is greatly beneficial for quality improvement and cost reduction.

BRIEF DESCRIPTION OF THE DRAWINGS It is drawing which shows an example of the frequency selective transmission type electromagnetic wave shielding material of this invention, (a) is a front view which shows schematic structure of a frequency selective transmission type electromagnetic wave shielding material, (b) is the partial expansion front of a metal mesh pattern. FIG. 4C is a partially enlarged cross-sectional view of a metal layer constituting the metal mesh pattern. It is a front view which shows the 2nd example of the frequency selective transmission type electromagnetic wave shielding material of this invention. It is the schematic which shows an example of the apparatus which performs electroless plating continuously following exposure and development by roll to roll. It is the schematic which shows an example of the apparatus which performs electroless plating and electrolytic plating continuously following exposure and development by roll to roll. It is the schematic which shows an example of the apparatus which performs electroless plating with a roll to roll. It is the schematic which shows an example of the apparatus which performs electroplating by a roll to roll. It is the schematic which shows an example of a continuous exposure apparatus. It is the schematic which shows another example of a continuous exposure apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Frequency selective transmission type electromagnetic wave shielding material, 2 ... Transparent base material, 3 ... Metal mesh pattern, 4 ... Metal layer, 4a ... Development silver layer, 4b ... Metal plating layer, 5 ... Slit, 10, 10A, 10B, DESCRIPTION OF SYMBOLS 10C ... Manufacturing apparatus, 11 ... Long base material, 12, 12A ... Original fabric roll, 13 ... Transfer roll, 14 ... Continuous exposure apparatus, 15 ... Developing apparatus, 16 ... Water washing tank, 17 ... Electroless plating tank, DESCRIPTION OF SYMBOLS 18 ... Electroless plating solution, 19 ... Receiving tank, 20 ... Circulation pump, 21 ... Filter, 22 ... Water washing tank, 23 ... Dryer, 25 ... Electrolytic plating tank, 26 ... Feeding roll, 27 ... Positive electrode plate, 28 DESCRIPTION OF SYMBOLS ... Electrolytic plating solution, 30 ... Continuous exposure apparatus, 31 ... Cylindrical drum, 32 ... Exposure mask part, 33 ... Light source for exposure, 34 ... Base material, 35 ... Light source cover, 40 ... Continuous exposure apparatus, 41 ... Cylindrical drum, 42 ... exposure mask film, 3 ... exposure light source, 44 ... substrate, 45 ... light source cover.

Claims (10)

A frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate,
The frequency selective transmission type electromagnetic wave shielding material, wherein the metal layer of the metal mesh pattern is composed of a developed silver layer produced by a photographic method and a metal plating layer laminated thereon.   The frequency selective transmission type electromagnetic shielding material according to claim 1, wherein the metal plating layer is an electroless plating layer and / or an electrolytic plating layer.   The frequency selective transmission electromagnetic wave shielding material according to claim 1 or 2, wherein the metal layer has a line width of 15 to 60 µm and a thickness of 0.5 to 15 µm.   4. The frequency selective transmission electromagnetic wave shielding material according to claim 1, wherein the surface of the metal plating layer is blackened.   The frequency according to any one of claims 1 to 4, wherein the developed silver layer is a developed silver layer produced by a positive photographic process or a developed silver layer produced by a negative photographic process. Selective transmission type electromagnetic shielding material. A method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate,
By exposing and then developing a base material on which at least one surface of the transparent base material is provided with a layer containing a substance that deposits metallic silver by exposure and development, a silver mesh layer having the slit is developed. A step of generating by
A method for producing a frequency selective transmission type electromagnetic wave shielding material, comprising at least a plating step of forming a metal plating layer on the developed silver layer. A method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate,
By exposing a base material provided with a layer containing a substance capable of depositing metallic silver by exposure and development to at least one surface of a long transparent base material using a continuous exposure apparatus, and then developing, A step of producing a raw roll in which a metal mesh pattern having a slit is generated by a developed silver layer;
After continuously unwinding the transparent substrate provided with the developed silver layer from the raw roll, a metal plated layer is formed on the developed silver layer by electroless plating and / or electrolytic plating, and wound up again. The manufacturing method of the electromagnetic wave shielding material of the frequency selective transmission type characterized by including the plating process used as a roll body at least. A method for producing a frequency selective transmission type electromagnetic shielding material in which a metal mesh pattern having a slit for transmitting electromagnetic waves of a predetermined frequency is disposed on at least one surface of a transparent substrate,
A substrate having a layer containing a substance that deposits metallic silver by exposure and development is continuously drawn on at least one surface of the long transparent substrate, and the transparent substrate is exposed using a continuous exposure apparatus. Then, by developing, a metal mesh pattern having the slit is generated by the developed silver layer, and subsequently, a metal plating layer is formed on the developed silver layer by electroless plating and / or electrolytic plating continuously. And the manufacturing method of the electromagnetic wave shielding material of a frequency selective transmission type characterized by winding up again to make a roll body.   The continuous exposure apparatus includes a cylindrical drum made of a material that transmits light used for exposure, an exposure mask portion provided on an outer peripheral wall of the cylindrical drum, and an exposure light source disposed inside the cylindrical drum. The frequency selective transmission type electromagnetic shielding material according to claim 7 or 8, wherein the transparent base material wrapped around the cylindrical drum is irradiated with light from the inside of the cylindrical drum. Production method.   The continuous exposure apparatus includes a cylindrical drum, an exposure mask film on which a continuous pattern is formed, and an exposure light source disposed outside the cylindrical drum, and a transparent substrate wound around the cylindrical drum. The method for producing a frequency selective transmission type electromagnetic shielding material according to claim 7 or 8, wherein the device and the exposure mask film irradiate light from outside the cylindrical drum.

Images