JP2003023290A - Electromagnetic wave shielding member and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electromagnetic wave shielding member which is adapted to have a resistance against mesh working by etching by not only incorporating a transparency and electromagnetic wave shielding properties but also eliminating discoloring of an adhesive in the meshing work by etching and upgrading an etching workability. SOLUTION: The electromagnetic wave shielding member comprises the mesh made of a metal foil stacked on one surface of a transparent film base via an adhesive in which a polyester polyurethane modified by a styrene/maleic copolymer and an aliphatic polyisocyanate are blended.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electromagnetic wave shielding member using a metal thin film (also referred to as metal foil) mesh and a method for manufacturing the same. More specifically, it is an electromagnetic wave shielding member using a metal thin film mesh for shielding an electromagnetic wave generated from an electromagnetic wave generation source such as a display electron tube, and the electromagnetic wave shielding member not only has its transparency and electromagnetic wave shielding property. It is characterized in that the discoloration of the adhesive in the mesh processing by etching is eliminated, the etching processability is improved, and the mesh processing by etching has resistance. Further, the present invention relates to an electromagnetic wave shielding member having improved contrast and good visibility. Further, if necessary, it cuts or absorbs near-infrared rays (light) generated from the inside of the display, and also absorbs a specific wavelength of visible light and / or near-infrared rays (light) by external light to improve contrast. The present invention relates to an electromagnetic wave shielding member having good visibility.

[0002]

2. Description of the Related Art Conventionally, an electronic device for generating an electromagnetic wave which a person directly approaches and uses, for example, an electronic tube for a display such as a plasma display, has a strong electromagnetic wave emission in consideration of a harmful effect of the electromagnetic wave on a human body. Is required to be within the standard. Further, in the plasma display panel (hereinafter also referred to as PDP), since the plasma discharge is used for light emission, the frequency band is 30 MHz to
Since unnecessary electromagnetic waves of 130 MHz are leaked to the outside, it is required to suppress the electromagnetic waves as much as possible so as not to adversely affect other devices (for example, information processing devices). In response to these requirements, in general, in order to remove or attenuate the electromagnetic waves that flow out from the electronic device that generates electromagnetic waves to the outside of the device, an electromagnetic wave shield that covers the outer peripheral portion of the electronic device that generates electromagnetic waves with an appropriate conductive member. Is taken. In a display panel such as a plasma display panel, it is common to provide an electromagnetic wave shielding plate having good transparency on the front surface of the display.

The electromagnetic wave shielding plate has a relatively simple basic structure, and a transparent conductive film such as an indium-tin oxide film (ITO film) is vapor-deposited or sputtered on a transparent glass or plastic substrate surface. Thin film formed with, such as a transparent glass or plastic substrate surface with a suitable metal screen such as wire mesh attached, transparent glass or plastic substrate surface, metal thin film over the entire surface by electroless plating or vapor deposition It is known that a metal thin film is formed and the metal thin film is processed by a photolithography method or the like to provide a mesh made of a fine metal thin film.

An electromagnetic wave shielding plate having an ITO film formed on a transparent substrate is excellent in transparency and generally has a light transmittance of about 90% and can form a uniform film on the entire surface of the substrate. Therefore, when used in a display or the like, there is no concern about the occurrence of moire or the like due to the electromagnetic wave shielding plate. However, in the electromagnetic wave shielding plate in which the ITO film is formed on the transparent substrate, since the technique of vapor deposition or sputtering is used to form the ITO film, the manufacturing apparatus is expensive and the productivity is generally inferior. Therefore, there is a problem that the price of the electromagnetic wave shielding plate itself as a product becomes expensive. Further, the electromagnetic wave shielding plate having the ITO film formed on the transparent substrate is inferior in conductivity to the electromagnetic wave shielding plate having the mesh formed of the metal thin film by one digit or more, so that the electromagnetic wave emission is relatively weak. It is effective for the target object, but when it is used for a strong target object, its shielding function becomes insufficient and leaked electromagnetic waves are emitted, which may cause the problem that the standard value cannot be satisfied. is there.
In the electromagnetic wave shielding plate in which the ITO film is formed on this transparent substrate, if the film thickness of the ITO film is increased in order to increase the conductivity, the conductivity is improved to some extent, but in this case, the transparency is significantly lowered. The problem occurs. in addition,
If the thickness is further increased, there is a problem that the manufacturing price becomes higher.

When an electromagnetic wave shielding plate having a transparent glass or plastic substrate surface with a metal screen is used,
Alternatively, when a suitable metal screen such as a wire mesh is directly attached to the display surface, it is simple and the cost is low, but an effective mesh (100-200 mesh) metal screen has a transmittance of 50 or less. % Or less,
It has the serious drawback of becoming an extremely dark display.

Further, a transparent glass or plastic substrate having a mesh formed of a metal thin film is externally processed by etching using a photolithography method, so that fine processing is possible and a high aperture ratio (high transmission) is achieved. rate)
Since the mesh can be created and the mesh is formed of a metal thin film, the conductivity is much higher than that of the ITO film and the like, and the advantage that strong electromagnetic wave emission can be shielded is provided. Have. However, avoiding the problem that the reflection of external light on the display panel cannot be absorbed, the visibility is poor, the manufacturing process is complicated and complicated, the productivity is low, and the production cost is high. I can't.

As described above, each electromagnetic wave shielding plate has its advantages and disadvantages, and is selected and used according to the application. Among them, the electromagnetic wave shielding plate in which a mesh made of a metal thin film is formed on the surface of a transparent glass or a plastic substrate is good in terms of electromagnetic wave shielding property and light transmitting property, and recently placed on the front surface of a display panel such as a plasma display panel. , Has come to be used for electromagnetic wave shielding. However, with conventional electromagnetic wave shields and displays,
In order to prevent malfunction of other devices, it cuts or absorbs near-infrared rays (light) generated from the inside of the display, and also improves the contrast. Since the absorbing function is laminated by separate steps,
There was a problem that the process was complicated, the productivity was poor, and it became thick.

An electromagnetic wave shielding member in which a mesh made of a metal thin film is formed on the surface of a transparent glass or plastic substrate is shown in FIG. 4 and will be briefly described. 4A is a plan view of the electromagnetic wave shielding member, and FIG. 4B is FIG. 4A.
FIG. 4C is a cross-sectional view taken along line A1-A2 of FIG. 4A and 4C show the X direction and the Y direction for clarifying the positional relationship and the mesh shape. The electromagnetic wave shielding member shown in FIG. 4 is an electromagnetic wave shielding member for an electromagnetic wave shielding plate placed on the front surface of a display such as a PDP, and has a grounding frame portion and a mesh portion formed on one surface of a transparent base material. The grounding frame part 415 is formed of the same metal thin film as the mesh part on the outer periphery of the mesh part 410 so as to surround the screen area of the display when placed on the front surface of the display. The mesh portion 410 has the shape shown in FIG.
As shown in a partially enlarged view in (c), it is composed of a plurality of line 470 groups and a plurality of line 450 groups provided in parallel with each other at predetermined pitches Px and Py in the Y and X directions. The mesh shape is not limited to that shown in FIG.

FIG. 5A shows an example of a mode in which the electromagnetic wave shielding plate 500 using the electromagnetic wave shielding member shown in FIG. 4 is placed on the front surface of the PDP and used, and FIG. 5B is shown. FIG. 6 is an enlarged cross-sectional view of an electromagnetic wave shielding (shield) region (corresponding to B0 portion) of FIG. 5A. Electromagnetic wave shielding plate 50
The electromagnetic wave shielding (shield) area of 0 (corresponding to B0 part) is
As shown in FIG. 5B, on the observer side of the transparent glass substrate 510, an NIR layer (near infrared absorption layer) 530 and an electromagnetic wave shielding member 4 shown in FIG.
00, a first AR layer (antireflection layer) film 540, and a second glass layer 510 on the transparent glass substrate 510 on the PDP 570 side.
The AR layer (anti-reflection layer) film 520 is provided. In FIG. 5, 500 is a front plate for a display,
Reference numeral 400 is an electromagnetic wave shielding member, 410 is a mesh portion, 43
0 is a transparent substrate, 510 is a glass substrate, 520 is the second A
R layer film, 521 film, 523 hard coat layer, 525 AR layer (antireflection layer), 527 antifouling layer, 530 NIR layer (near infrared absorbing layer), 540 first AR layer film, 541 is a film, 543 is a hard coat layer, 545 is an AR layer (antireflection layer), 547 is an antifouling layer, 551, 553, 555 is an adhesive layer, 570 is a PDP (plasma display), 571 is a mounting boss, and 573. Is a screw, 572 is a base, 574 is a mounting bracket, 575 is a front part of the housing, 576 is a rear part of the housing, and 577 is a housing. The positions of the NIR layer (near-infrared absorbing layer) and the electromagnetic wave shielding member are not particularly limited to those shown in FIG. 5B, and a colored layer for color adjustment may be provided if necessary. Also, conventionally, as a method for adhering an electromagnetic wave shielding member to a transparent substrate, it has been proposed in JP-A-11-307988 to use an adhesive composed of an ethylene vinyl acetate copolymer. In particular, it was obvious that the adhesive required for the electromagnetic wave shielding member for displays had high adhesive strength and high transparency, but the adhesive discolored due to lack of resistance to mesh processing by etching. was there.

[0010]

Therefore, an electromagnetic wave shielding member for an electromagnetic wave shielding plate provided on a transparent substrate with a mesh made of a metal thin film as shown in FIG.
It is an object of the present invention not only to have the transparency and the electromagnetic wave shielding property, but also to eliminate the discoloration of the adhesive in the mesh processing by etching, improve the etching processing property, and have the resistance to the mesh processing by etching. Another object is to provide an electromagnetic wave shielding member having excellent visibility. Furthermore, if necessary, with a layer structure as small as possible, it cuts or absorbs near-infrared rays (light) generated from the inside of the display, and also absorbs a specific wavelength of visible light by light emission or outside light inside the display, It is also an object to improve the contrast of the malfunction of other devices or the image of the display screen and the like to provide good visibility.

[0011]

An electromagnetic wave shielding member, a method for manufacturing the same, and a display, which are means for solving the problems of the present invention, will be described below with reference to the drawings. FIG. 10 is a perspective view showing an example of the layer structure of the electromagnetic wave shielding member 4000 of the present invention. (Example 1) FIG. 11 shows a case where the electromagnetic wave shielding member 4000 of FIG.
It is a sectional view showing an example of a vertical section layer composition at the time of being cut by a plane parallel to a 000 mesh. (Example 1) FIG.
FIG. 12 is a schematic cross-sectional view showing a state before etching of the copper foil 1000 to which the copper bump 1300 constituting the electromagnetic wave shielding member 4000 of FIG. 11 is attached. FIG. 7 is a cross-sectional view showing an example of the layer structure of the electromagnetic wave shielding member of the present invention. FIG. 8 is a cross-sectional view showing another example of the layer structure of the electromagnetic wave shielding member of the present invention. FIG. 9 is a schematic sectional view showing an example of a display in which the electromagnetic wave shielding member of the present invention is laminated. The characteristics of the electromagnetic wave shielding member of the present invention and the manufacturing method thereof are described in (1) to (13). (1) A mesh made of a metal thin film is laminated on one surface of a transparent film substrate through an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. It is what (FIGS. 10 to 11) By using an adhesive compounding a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate as an adhesive agent for a metal mesh and a transparent film, etching processability can be improved. It is intended to provide a good electromagnetic wave shielding member. (2) In (1), the transparent film substrate is polyethylene terephthalate, and the metal foil has a thickness of 5 μm.
˜20 μm. The thickness of the metal foil is 5
A fine pattern mesh shape could be created by setting the thickness to be 20 μm to 20 μm. The thickness of the metal foil is 5
If it is less than μm, fine pattern processing becomes easy, but the electric resistance value of the metal increases, and the electromagnetic wave shielding effect is impaired. On the other hand, when the thickness is 20 μm or more, it is difficult to obtain a fine pattern mesh shape, the aperture ratio is substantially lowered, the transmittance is lowered, and the viewing angle is narrowed.
That is, the thickness of the metal foil is set to 5 μm to 20 μm to provide an electromagnetic wave shielding member having excellent visibility. (3) In (1) or (2), the metal foil is a copper foil, and at least one surface of the metal foil has been subjected to a roughening treatment by depositing copper bumps by cathodic electrodeposition, Is characterized in that at least one surface thereof is subjected to anticorrosion chromate treatment. (By this,
An electromagnetic wave shielding member having excellent visibility is provided. ) (FIGS. 11 to 12) When the metal foil is a copper foil, a copper bump is attached by cathodic electrodeposition. The purpose and method of attaching copper bumps by cathodic electrodeposition will be described in detail. Purpose: In order to improve visibility, it is better to subject the observation side surface of the mesh pattern to blackening treatment. This improves the sense of contrast. Method: A copper foil is subjected to cathodic electrolysis in an electrolytic solution containing sulfuric acid / copper sulfate to deposit cationic copper particles. By using a copper foil as the metal foil, it becomes possible to attach a copper lump by cathodic electrodeposition, a black color which has not been obtained until now is obtained, and the contrast feeling of the display is increased. In addition, rust-preventive chromate treatment (simply referred to as chromate treatment) was performed to improve handleability and prevent quality deterioration due to rust. (4) It is characterized in that the transparent film substrate is adhered to the surface of the copper foil of (3) where copper lumps are attached by cathodic electrodeposition. (Fig. 11) (5) Laminate a metal foil on a transparent film substrate with an adhesive compounded with polyester polyurethane modified with a styrene / maleic acid copolymer and aliphatic polyisocyanate, and etch the metal foil of the laminated member. A method for producing an electromagnetic wave shielding member, which is obtained by processing and forming a mesh. In this way, by laminating the metal foil on the transparent film base material and etching the metal foil of the laminating member to form a mesh, a good quality electromagnetic wave shielding member is provided. (6) The method of manufacturing an electromagnetic wave shielding member, wherein the etching treatment of (5) uses ferric chloride as an etching solution.

(7) A styrene / maleic acid copolymer containing a mesh composed of a metal thin film and an absorber for absorbing a specific wavelength of visible light and / or near infrared is contained on one surface of a transparent film substrate. An electromagnetic wave shielding member, which is laminated through an adhesive containing a polyester polyurethane modified with a polymer and an aliphatic polyisocyanate. Near infrared generally refers to a region of 780 nm to 1000 nm, and it is desirable that the absorptance in this wavelength region is 80% or more. -As the absorber that absorbs a specific wavelength in the near infrared, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, zinc oxide, iron oxide, antimony oxide,
Inorganic infrared absorbers such as lead oxide and bismuth oxide, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, diimonium compounds, nickel complexes, dithiol complex organic infrared absorbers, etc. Can be used. The inorganic infrared absorber is preferably fine particles and has an average particle size of 0.005.
The average particle size is preferably in the range of 0.01 to 0.5 μm.
The fine particles of the inorganic infrared absorbent preferably have a particle size distribution of 1 μm or less in order to improve the visible light transmittance. The infrared absorbent is preferably dispersed in a highly dispersed state. -The absorber that absorbs visible light is a metal absorber and a pigment absorber described later. (8) A metal thin film mesh is laminated on one surface of a transparent film substrate via an adhesive containing polyester polyurethane modified with a styrene / maleic acid copolymer and aliphatic polyisocyanate, and the metal thin film is formed. In the member for electromagnetic wave shielding, in which a layer for flattening the uneven surface of a mesh made of is laminated, at least one of the flattening layer and the adhesive is an absorber that absorbs a specific wavelength of visible light and / or near infrared. An electromagnetic wave shielding member containing.
(FIGS. 7 to 9) (9) A transparent film substrate is provided on one side with a mesh composed of a metal thin film through an adhesive agent containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. An electromagnetic wave shielding member in which a layer for flattening the uneven surface of the mesh made of the metal thin film is laminated, and an adhesive or pressure-sensitive adhesive is laminated on at least one surface of the flattening layer or the transparent film substrate. In the electromagnetic wave shielding member described above, an electromagnetic wave shielding member in which at least one of the flattening layer, the adhesive or the pressure-sensitive adhesive contains an absorber that absorbs a specific wavelength of visible light and / or near infrared. (FIGS. 7 to 9) (10) An electromagnetic wave shielding member obtained by laminating the above electromagnetic wave shielding member and a visible light absorbing layer and / or a near infrared absorbing layer. (Visible Light Absorption Layer) The absorption layer in the visible light region (380 to 780 nm) is provided for the purpose of balancing the color of the display or absorbing external light to improve the contrast. The visible light absorption layer has a transmittance of 50% to 9%.
8% is preferable. As the metal absorbent, for example, N
d, Au, Pt, Pd, Ni, Cr, Al, Ag, In
One type of metal such as 203-SnO2, CuI, CuS, and Cu, or a combination of two or more types of metals is used. These may be formed into a visible light absorbing layer by vapor deposition, CVD, sputtering or the like. Known pigments can be used as the pigment absorbent. Specifically, phthalocyanine type, azo type, condensed azo type, azo lake type, anthraquinone type, perylene / perinone type, indigo / thioindigo type, isoindolino type, azomethine azo type, dioxyzan type, quinacridone type, aniline black type, triphenylmethane. Series, organic pigments such as carbon black series, neodymium compound series, titanium oxide series, iron oxide series, iron hydroxide series, chromium oxide series, spinel type firing system,
Examples thereof include chromic acid type, chrome vermillion type, dark blue type, aluminum powder type, bronze powder type and the like. (11) An electromagnetic wave shielding member obtained by stacking the above electromagnetic wave shielding member and an antireflection layer and / or antiglare layers 1 and 7. (FIGS. 7 to 9) (12) An electromagnetic wave shielding member obtained by laminating the above electromagnetic wave shielding member and a glass or acrylic transparent substrate 2.
(FIGS. 7 to 9) (13) A display 30 in which the above electromagnetic wave shielding member is directly laminated on the surface of the display. (Figure 9)

In addition, the above-mentioned member for electromagnetic wave shielding plate,
Chromate treatment, metal oxide, metal sulfide on at least one surface through an adhesive compounded with polyester polyurethane modified with a styrene / maleic acid copolymer and aliphatic polyisocyanate on one surface of a transparent film substrate It is characterized in that a mesh made of a metal thin film, which has been blackened by a method such as the above, is laminated. With such a structure, an electromagnetic wave shielding member having electromagnetic wave shielding properties and transparency is obtained. In addition, by subjecting the surface blackening treatment for absorbing external light to chromate treatment, it is possible to obtain a blackening treatment layer having a high black density and high adhesiveness with a metal. Further, in the above, the black density of the chromate-treated surface of the metal thin film mesh is 0.6 or more. In order to absorb outside light and obtain good visibility, the black density of the chromate-treated surface of the metal thin film mesh is 0.
It is preferably 6 or more. All black density measuring methods in the present invention are performed by KIMOTO COLO.
G RETAG S of R CONTROL SYSTEM
The measurement was performed using PM100-11. As the measurement conditions, an observation visual field of 10 degrees, an observation light source D50, and an illumination type of density standard ANSI T were set, and each sample was measured after white calibration.

The electromagnetic wave shielding member of the present invention is, for example, by the following method for producing an electromagnetic wave shielding member of the present invention,
It is characterized by being manufactured. However, in the method for producing an electromagnetic wave shielding member of the present invention, the mesh made of a metal thin film is not necessarily blackened by chromate treatment, but preferably at least one surface is blackened by chromate treatment. It is preferable to use a mesh made of a thin metal film that has been treated. Therefore, in the following method for manufacturing an electromagnetic wave shielding member of the present invention, the case where the blackening treatment is performed by the chromate treatment will be mainly described. (A) The method for producing an electromagnetic wave shielding member according to the present invention is a member for an electromagnetic wave shielding plate that is used by being placed on the front surface of a display (may be directly attached to the display), and is provided on one surface of a transparent film substrate. A mesh consisting of a metal thin film, at least one surface of which has been blackened by chromate treatment, is laminated through an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. A method for producing an electromagnetic wave shielding member having electromagnetic wave shielding properties and transparency, comprising: (a) a styrene / maleic acid copolymerization wherein a belt-shaped continuous metal foil and a belt-shaped continuous film substrate are used. Bonded with a polymer-modified polyester polyurethane and an aliphatic polyisocyanate adhesive to form a strip And (b) etching the metal foil of the laminated member to form a mesh or the like in sequence while continuing the laminated member forming process for forming the laminated member and continuously or intermittently conveying the laminated member. , A masking treatment for continuously or intermittently forming an etching resistant resist mask along the longitudinal direction so as to cover the surface of the metal foil that is not on the film substrate side, and (c) exposing it from the opening of the resist mask. The metal foil portion is etched to form a mesh or the like made of a metal thin film, and an etching treatment is performed. Here, in the above (a), prior to the laminating treatment, blackening treatment is performed by chromate treatment on both sides or one side of the copper foil or the metal foil made of an iron material in advance.
A copper bump may be attached to the copper foil before the chromate treatment. However, prior to the laminating treatment, if both sides or one side of the metal foil made of copper foil or iron material is not subjected to blackening treatment by chromate treatment, in (a) above, after etching treatment, resist After removing the pattern by peeling and performing a cleaning treatment as necessary, the exposed mesh surface of the metal thin film is subjected to a blackening treatment by a chromate treatment or the like.

Further, in the above (a), after the etching treatment, the mesh surface made of the metal thin film may optionally contain an absorbing agent for absorbing a specific wavelength of visible light and / or near infrared. With an adhesive layer or an adhesive layer, and a silicon separator (silicone treated for easy peeling P
It is characterized by performing a laminating process for laminating an ET film). And again (above)
In the step of forming a laminated member, the strip-shaped continuous film base is coated on the surface of the strip-shaped film substrate with an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. Then, laminating is performed, and the metal foil and the film substrate are bonded together to form a continuous strip-shaped laminated member, which is a laminating process. The film base material 11 that requires an adhesive or the like during the laminating process
Examples of 0 include polyester and polyethylene, and examples of the film substrate 110 that does not necessarily require an adhesive at the time of lamination treatment include ethylene vinyl acetate, ethylene acrylic acid resin, ethylene ethyl acrylate, and ionomer resin.

Alternatively, in the above-mentioned (a), the laminated member forming treatment is performed by coating a resin on one surface of the continuous metal foil in a strip shape by a coating method such as extrusion coating or hot melt coating.
It is characterized by being formed. still,
Examples of the extrusion coating material include polyolefin and polyester. Examples of the hot-melt coating material include a resin mainly containing ethylene vinyl acetate, a resin mainly containing polyester, and a resin mainly containing polyamide.

In the above, the metal foil has a thickness of 1 μm to
A copper foil or an iron material having a thickness of 100 μm, which is characterized in that the etching treatment uses a ferric chloride solution as an etching solution. Further, in the above, the transparent film substrate is a PET film (polyethylene terephthalate film).

In the masking treatment described above, the surface of the metal foil is coated with a resist, dried, and then the resist is contact-exposed with a predetermined pattern plate, and a development process is performed to form a resist pattern of a predetermined shape on the metal foil surface. And the resist pattern is subjected to a baking treatment, if necessary.

Further, in the above, the functions not imparted to the colored adhesive layer may be laminated as a film separately laminated. For example, after laminating a silicon separator (silicone-treated, easily peelable PET film), a NIR layer (near infrared absorption layer) is formed on one side of the film on the non-mesh side of the transparent film substrate. The NIR layer film described above and the AR layer film having an AR layer (antireflection layer) formed on one surface of the film are laminated in this order, and the laminating step is a transparent film substrate. After laminating the NIR layer film via the adhesive layer on the surface not on the mesh side of the material,
Further, the AR layer film is laminated on the NIR layer film via an adhesive layer, and at least one of the adhesive or the pressure-sensitive adhesive absorbs a specific wavelength of visible light and / or near infrared. It is also characterized in that it contains an absorbent.

[0020]

According to the method of manufacturing an electromagnetic wave shielding member of the present invention, by virtue of such a constitution, a specific wavelength of visible light and / or near infrared light provided with a metal thin film mesh used for an electromagnetic wave shielding plate is provided. It is a method of manufacturing an electromagnetic wave shielding member with good absorption performance and good visibility, and it can sufficiently cope with quality.
It is possible to provide a manufacturing method with good productivity. As a result, an electromagnetic wave shielding plate for a display such as a PDP as shown in FIG. 4 which has a property of absorbing a specific wavelength of visible light and / or a near infrared ray, good visibility, transparency and electromagnetic wave shielding property is provided. It is supposed that a large amount can be provided early.

Specifically, as an example, (a) a strip-shaped continuous chromate-treated metal foil and a strip-shaped continuous film substrate are polyester polyurethane modified with a styrene / maleic acid copolymer and aliphatic. A laminate member forming process for forming a laminate member that is bonded and continuous in a strip shape via an adhesive compounded with polyisocyanate, and while continuously or intermittently conveying the laminate member, (b) the above An etching-resistant resist mask for etching the metal foil of the laminated member to form a mesh or the like is provided continuously or intermittently along its longitudinal direction so as to cover the surface of the metal foil that is not the film substrate side. The masking process to be performed and (c) the metal foil portion exposed from the opening of the resist mask is etched to form a mesh made of a metal thin film, etc. Formed by having an etching process, and further, after the etching process,
If necessary, an adhesive layer or a flattening layer containing an absorber that absorbs a specific wavelength of visible light and / or near-infrared is provided on a mesh surface made of a metal thin film.
This is made possible by performing a laminating process of laminating a separator (silicone-treated easily peelable PET film). That is, the masking process and the etching process can be performed in an integrated line, as in the case of producing a shadow mask for a cathode ray tube of a color TV from a strip of steel material.

Then, the laminated member is formed into a belt-like shape through an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate on the surface of the film substrate which is continuous in a belt shape. Laminating a continuous metal foil, the metal foil and the film substrate are bonded to each other to be continuous in a strip shape, in the case of a laminating process to form a laminated member, the work is simple, the metal foil, continuously, Etching can be performed with good productivity. In particular, the masking treatment is to apply a resist on the surface of the metal foil, and after drying, contact-expose the resist with a predetermined pattern plate, and through a development treatment, form a resist pattern of a predetermined shape on the metal foil surface, By subjecting the resist pattern to a baking process as required, fine plate-making with a resist can be performed, and it is possible to cope with quality as well as mass production.

(Metal Foil) The surface roughness of the metal foil is J
0.5 in ten-point average roughness Rz according to IS B0601
If the thickness is less than or equal to μm, the external light is specularly reflected even if the blackening treatment is performed, and the visibility is deteriorated. On the contrary, JIS B0
If the ten-point average roughness Rz according to 601 is 10 μm or more, it is difficult to apply an adhesive, a resist, or the like.
The surface roughness of the (electrolytic) metal foil can be obtained by controlling the surface roughness of the metal roll used in the production.
As the metal of the metal foil, copper, iron, nickel, chromium and the like, but not particularly limited, copper is copper nodule adhesion by cathodic electrodeposition, electromagnetic wave shielding, etching treatment suitability and handleability. Most preferred. As the copper foil, a rolled copper foil or an electrolytic copper foil can be used. Particularly, the electrolytic copper foil can have a thickness of 10 μm or less, has good thickness uniformity, and has good adhesion to chromate treatment. preferable. It is advisable to attach a copper bump to the copper foil before the chromate treatment. In addition, the metal foil is an iron material (low carbon steel, Ni-Fe alloy)
From the above, it is possible to produce a material which is particularly excellent in electromagnetic wave shielding property. As the iron material, low carbon steel containing almost no Ni (low carbon rimmed steel, low carbon aluminum killed steel, etc.) is preferable in terms of etching treatment, but is not limited thereto. If the thickness of the metal foil becomes thicker, it is difficult to make the pattern line width finer and finer by side etching.

In the etching treatment of the metal foil, the ferric chloride solution is used as the etching solution, so that the etching solution can be easily circulated and the etching treatment can be easily performed continuously on an integrated line. . When the iron material is a Ni—Fe alloy such as Invar material (42% Ni—Fe alloy), Ni is mixed in the etching solution,
It is necessary to manage the etching solution corresponding to this.

In the present invention, prior to the laminated member forming process,
It is possible to prevent reflection on the blackened surface of the metal foil by performing blackening treatment by chromate treatment on both sides or one side of the metal foil made of copper foil, iron material or the like in advance. It is advisable to attach a copper bump to the copper foil before the chromate treatment. In particular, when blackening treatment is performed by chromate treatment on both sides or one side prior to the laminated member forming treatment, it is not necessary to perform blackening treatment by chromate treatment afterwards, resulting in good workability. . Prior to the laminated member forming treatment, if the blackening treatment is not performed on both sides or one side of the metal foil made of the copper foil or the iron material in advance, the resist pattern is peeled and removed after the etching treatment. After performing the cleaning treatment accordingly, the exposed mesh surface of the metal thin film is subjected to the blackening treatment by the chromate treatment, but the workability is poor. Chromatization is performed not only on the viewing side but also on the display side,
It is more preferable because stray light from the display can be prevented.

The chromate treatment is to apply a chromate treatment liquid to the material to be treated. The treatment liquid is applied to the material to be treated by, for example, a roll coat method, an air-curtain method, an electrostatic atomization method, a squeeze roll coat method, a dipping method, etc., and dried without washing with water. Method. In the present invention, the material to be treated is a mesh made of the metal foil or metal thin film described above. As a chromate treatment liquid, CrO2 is 3 g / l
Aqueous solutions containing are usually used. In addition, "chromate treatment liquid obtained by adding different oxycarboxylic acid compounds to chromic anhydride aqueous solution to reduce part of hexavalent chromium to trivalent chromium"
Can also be used. As a specific chromate treatment, Cr
The metal foil was immersed in an aqueous solution (25 ° C.) containing 3 g / l of O 2 for one second or the whole for 3 seconds. Alternatively, as another chromate treatment, different oxycarboxylic acid compounds are added to an aqueous solution of chromic anhydride, and a chromate treatment liquid obtained by reducing a part of hexavalent chromium to trivalent chromium is rolled on a metal foil.
It was applied by the rukot method and dried at 120 ° C.

Examples of the oxycarboxylic acid compound include tartaric acid, malonic acid, citric acid, lactic acid, gluconic acid, glyceric acid, tropic acid, benzylic acid and hydroxyvaleric acid, and these reducing agents are used alone or You may use together. Since the reducibility varies depending on the compound, the addition amount is performed while grasping the reduction to trivalent chromium.

The transparent film base material is a PET film (polyethylene terephthalate film) so that it can withstand each process.

After laminating with a silicon separator (silicone-treated, easily peelable PET film), a NIR layer (near infrared absorption layer) is formed on one side of the film on the non-mesh side of the transparent film substrate. By having a laminating step of laminating the formed NIR layer film and the AR layer film having an AR layer (antireflection layer) formed on one surface of the film in this order, in addition to the electromagnetic wave shielding function, a further near infrared absorbing function, It is possible to manufacture an electromagnetic wave shielding member (front protective plate for a display) having an antireflection function. In addition to this, the electromagnetic wave shielding member (front protection plate for display) may have the layer structure as shown in FIGS.

As shown in FIGS. 3 (c) and 3 (d),
It is preferable that the adhesive layer 135 or the adhesive layer in the mesh opening portion formed of the metal thin film is a flattening (planarizing) layer, but as shown in FIG. Due to the roughened surface, the transparency is poor and the unevenness of the mesh made of a metal thin film makes it difficult to stick when laminated on a front panel such as glass, an antireflection layer, or a display. Before forming the layer or adhesive layer
It is desirable to apply a resin on the mesh side made of a metal thin film to form a planarizing (planarizing) resin layer 6.
(See Fig.7 to Fig.9) And, during coating, it is necessary to devise a method to prevent bubbles from remaining in the corners of the mesh consisting of a metal thin film, and not to deteriorate the transparency. A coating method in which the resin is laminated while drying or deaerating air is desirable. Such a flattening resin has high transparency and good adhesiveness to an adhesive for dry lamination or a copper mesh, and this flattening resin layer has a specific visible light and / or near infrared ray. When an absorber that absorbs a wavelength is contained, it is preferable that it has excellent dispersibility with each absorber. The surface of the flattening resin layer is particularly important from the viewpoint of preventing moire and interference unevenness with the display, and it is preferable that there be no protrusions, dents, unevenness or the like as much as possible. For example, apply resin or
It is also possible to obtain a resin layer having excellent flatness by coating and then laminating it on a substrate having excellent flatness and then curing the resin by heat or light to peel off the substrate. As a resin,
It is not particularly limited as long as it satisfies the above characteristics, but coatability, hard coat property, easiness of flattening, and the like,
Acrylic UV curable resins are preferred. Further, by imparting tackiness or adhesiveness to such a resin, it is possible to form a tacky layer or an adhesive layer having excellent flatness, thereby reducing the number of layers and the manufacturing process.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a manufacturing process flow chart showing an embodiment of a method for manufacturing an electromagnetic wave shielding member of the present invention,
2 is a partial cross-sectional view for explaining a masking process, an etching process, and a laminating process for laminating a silicon separator (silicone-treated easily peelable PET film), and FIG. 3A is formed with a laminating member. FIG. 3B is a diagram showing the positional relationship between the mesh part of the electromagnetic wave shielding member and the grounding frame part, and FIG. 3B is a diagram showing the mesh part and the grounding frame part. FIG. 3D is a cross-sectional view showing the layer structure of the electromagnetic wave shielding member to be produced. 2A, 2B, 3C, and 3D are similar to FIG.
It is sectional drawing in the P1-P2 position of (b). Figure 1,
2 and 3, 110 is a film base material, 120 is a metal foil, 120A is a mesh portion, 120B is a grounding frame portion, 1
20C is a processed part, 130 is an adhesive layer, 135 is an adhesive layer,
140 is a silicon separator (protective film), 1
50 is an NIR layer film, 151 is a film, 152 is an NIR layer, 160 is an AR layer film, 161 is a film, 162 is a hard coat layer, 163 is an antireflection layer, 1
64 is an antifouling layer, 170 and 175 are adhesive layers, and 190 is a laminated member (laminate member). Incidentally, in FIG. 1, S11
0 to S220 indicate processing steps. Figure 6
FIG. 3 is a cross-sectional view showing two examples of the layer structure of the metal foil 120 of FIG. FIG. 6A is a cross-sectional view showing the metal foil 120 having a chromate layer (blackening layer) 122 on one surface of the metal layer 121. FIG. 6B is a cross-sectional view showing the metal foil 120 having the chromate layer (blackening layer) 122 on both surfaces of the metal layer 121.

First, a first example of an embodiment of a method for manufacturing an electromagnetic wave shielding member of the present invention will be described with reference to FIG. This example is a member shown in FIG. 5 for producing an electromagnetic wave shielding plate for an electromagnetic wave shield placed on the front surface of a display such as a PDP. One surface of a transparent film substrate is treated with a chromate treatment. As a metal foil for forming a mesh made of a metal thin film by a manufacturing method for mass-producing an electromagnetic wave shielding member that has been subjected to blackening treatment and has a mesh made of a metal thin film and has electromagnetic wave shielding properties and transparency. A copper foil or iron material (low carbon steel) having a thickness in the range of 1 μm to 100 μm is used. First, a continuous film base material (S110) supplied in a rolled-up state is stretched without looseness (S11).
1) and a continuous (chromate-treated) metal foil (S120) supplied in a rolled-up state
In a state of being stretched without slack (S122), and on one surface of the film substrate 110 continuous in a strip shape, through an adhesive compounding a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate,
The metal foil 120 continuous in a strip shape is laminated (S13
0), the laminating member 190 in which the film base material 110 and the metal foil 120 are bonded to each other and continuous in a strip shape is formed. (S140) Lamination can be performed with a laminating roll having a pair of two rolls.

In this example, the metal foil 120 is made of copper foil or iron material (low carbon steel containing almost no Ni), and blackened by a chromate treatment (S115 or S121) before laminating. Is blackened to form a chromate layer 122. (See (b) of FIG. 6 and FIG. 1) Here, before the lamination, the continuous metal foil is usually supplied in a rolled-up state (S120).
Is to perform the chromate processing S115 off-line in advance. However, if the continuous metal foil (S120) supplied in a rolled-up state is not subjected to the chromate treatment S115 off-line in advance, the chromate treatment S121 is performed in-line in the preceding step of the laminating step. You can keep it. The blackening treatment was performed by a chromate treatment by immersing the metal foil 120 in an aqueous solution (25 ° C.) containing 3 g / l of CrO 2 for 3 seconds.

The film substrate 110 is not particularly limited as long as it has good transparency, withstands processing, and has good stability, but a PET film is usually used. In particular,
The biaxially stretched PET film is preferable because it has good transparency, chemical resistance and heat resistance. As described above, polyester, polyethylene or the like may be used as the film substrate 110 that requires an adhesive or a pressure-sensitive adhesive during the laminating process S130.
Examples of the film substrate 110 that does not require an adhesive include ethylene vinyl acetate, ethylene acrylic acid resin, ethylene ethyl acrylate, and ionomer resin.

(Adhesive) In the present invention, the adhesive provided between the transparent film substrate and the mesh composed of the metal thin film is a styrene / maleic acid copolymer which does not stain or deteriorate with an etching solution. An adhesive containing a modified polyester polyurethane and an aliphatic polyisocyanate is used. In the present invention, the adhesive provided in a place other than between the transparent film substrate and the mesh made of a metal thin film is not particularly limited,
Adhesives containing polyester polyurethane modified with styrene / maleic acid copolymers and aliphatic polyisocyanates, acrylic resins, polyester resins, polyurethane resins, polyvinyl alcohol alone or partially saponified products (brand name Poval), chlorinated Adhesive of thermosetting resin or UV curable resin is preferable from the viewpoint of post-processing, laminating and coating properties such as vinyl-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, dyeing with an etching solution, and little deterioration. . In particular, a polyester resin is also preferable from the viewpoints of adhesion with a transparent polymer substrate, compatibility with the above-mentioned visible light absorber and infrared absorber (also referred to as near infrared absorber), dispersibility and the like. In order to have visible light and / or near-infrared absorbing ability, in each adhesive, if necessary,
It is advisable to mix and disperse an absorbing agent (visible light absorbing agent, near infrared absorbing agent) that absorbs a specific wavelength of visible light and / or near infrared. As a method of forming the adhesive layer, a film substrate is coated with various coating methods such as a roll coater, a Meyer bar and a gravure to have a thickness of 1 to 100 μm.

Examples of the adhesive include natural rubber type, synthetic rubber type, acrylic resin type, polyvinyl ether type, urethane resin type, silicone resin type and the like. Specific examples of synthetic rubber include styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NB
R), polyisobutylene rubber, isobutylene-isoprene rubber, isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer,
A styrene-ethylene-butylene block copolymer is mentioned. Specific examples of the silicone resin type include dimethyl polysiloxane and the like. These adhesives have 1
They may be used alone or in combination of two or more.

In order to have the ability to absorb visible light and / or near-infrared light, the pressure-sensitive adhesive may contain, if necessary, an absorbent that absorbs a specific wavelength of visible light and / or near-infrared light (visible light absorption). It is advisable to mix and disperse the agent and the near infrared absorber).
It is advisable to further mix and disperse a tackifier, a filler, a softening agent, an antioxidant, an ultraviolet absorber, a cross-linking agent, etc. in the pressure-sensitive adhesive, if necessary. As a method for forming the adhesive layer,
1 to 10 by various coating methods such as roll coater, Meyer bar and gravure for the film substrate.
It is formed by coating to a thickness of 0 μm, preferably 10 to 50 μm.

Next, while the laminated member 190 is continuously or intermittently conveyed and stretched without looseness, the metal foil of the laminated member is sequentially etched to form a mesh or the like. The resist mask is continuously or intermittently formed along the longitudinal direction of the metal foil (S150), and the metal foil portion exposed from the resist mask is etched to form a mesh made of a metal thin film. Then, etching processing (S160) is performed. As shown in FIG. 3A, etching processing portions 120C such as a mesh are formed by imposition on a metal foil in the longitudinal direction of the laminate member 190 at predetermined intervals. In the present example, the etching processed portion 120C is shown in FIG.
The mesh part 120A and the grounding frame part 120B shown in (b)
Shall consist of The mesh part 120A is an electromagnetic wave shielding region.

As the masking treatment, for example, a photosensitive resist such as casein or PVA is coated on the metal foil 120 (S151), dried (S152), and then contact-exposed with a predetermined pattern plate (S153). Water development (S15
4), the film is hardened and baked (S15).
5), a series of processes. The resist is usually applied on one or both sides (metal foil side) of a water-soluble casein, PVA, gelatin or the like by dipping (dipping), curtain coating or pouring while transporting the laminate member. . In the case of casein resist, it is preferable to perform baking at about 200 to 300 ° C., but in order to prevent the laminate member 190 from warping or curling, the treatment temperature is lowered as much as possible and curing is performed. When the dry film resist is a photosensitive resist, the workability of the resist coating step (S151) can be improved. In addition, the etching treatment uses a ferric chloride solution as an etching solution, which makes it easy to circulate the etching solution and facilitate continuous etching treatment.

In this example, the masking process (S150) and the etching process (S160) are performed with the laminate member 190 stretched without looseness. The masking process (S150) and the etching process (S160) are strip-shaped. This is basically the same as the case where a shadow mask for a cathode ray tube of a color TV, in particular, a thin plate (20 μm to 80 μm) is produced by etching from one surface from a continuous steel material.
That is, the masking process and the etching process can be performed on an integrated line, and the metal foil of the laminate member in which the metal foil and the film are bonded to each other and continuous in a strip shape can be continuously and efficiently etched.

Then, after the etching process (S160),
An adhesive layer (corresponding to 135 in FIG. 3) that also serves as a flattening layer is provided on the surface of the metal foil on which the mesh has been formed after washing, etc., and a silicon separator (silicone-treated easily peelable PET film) ) Is laminated. (S18
0) As the adhesive forming the adhesive layer, the same adhesives as described above can be used. The adhesive layer is provided by a roll coater, die coater, blade coater, screen printing or the like. When used as an electromagnetic wave shielding plate, the silicon separator is peeled off from the adhesive layer and is a temporary protective film. This state is the electromagnetic wave shielding member having the layer structure shown in FIG.

Next, after laminating the NIR layer film 150 via the adhesive layer (S190), the AR layer film 160 is further laminated thereon via the adhesive layer. (S200) As the adhesive forming each adhesive layer, the same adhesive as the above-mentioned adhesive can be used. For example, an acrylic material having good transparency is used. Examples of commercially available products include an adhesive (manufactured by Lintec Co., product number PSA-4).

NIR layer film (150 in FIG. 3 (d))
Is a film in which a NIR layer (near infrared absorption layer) is provided on a transparent film. In the commercially available film, No 2832 manufactured by Toyobo Co., Ltd., which is a polyethylene terephthalate (PET) film coated with an NIR layer, is generally used. Are known. Near infrared is generally 780 nm to 1000
It indicates the region of nm, and it is desirable that the absorptance in this wavelength region is 80% or more. The NIR layer (near infrared absorption layer) is not particularly limited, but has a sharp absorption in the near infrared region, a high light transmittance in the visible region, and a large absorption of a specific wavelength in the visible region. There is no such thing.
A layer in which one or more kinds of dyes having a maximum absorption wavelength at a light wavelength of 800 nm to 1000 nm are dissolved in a binder resin is used as the NIR layer (near infrared absorption layer), and the thickness thereof is about 1 to 50 μm. Examples of the dye include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, and dithiol complexes. As the binder resin, polyester resin, polyurethane resin, acrylic resin or the like is used. A cross-linking type binder using a reaction of epoxy, acrylate, methacrylate, isocyanate group, etc. by ultraviolet rays or heating is also used. As a solvent for coating, a cyclic ether or ketone capable of dissolving the above-mentioned dye, for example, tetrahydrofuran, dioxane, cyclohexane, cyclopentanone or the like is used.

The AR layer film is usually 1 in FIG. 3 (d).
It is a film having a layer structure as shown in 60 and having an AR layer provided on a transparent film. The AR layer (antireflection layer) is for preventing the reflection of visible light, and its structure is known to be various layers such as a single layer and a multilayer. As the multilayer, a high refractive index layer and a low refractive index layer are known. A structure in which the layers are alternately laminated is common. The material of the antireflection layer is not particularly limited. The antireflection layer is produced by a Dry method such as sputtering or vapor deposition, or by wet coating. still,
Examples of the high refractive index layer include niobium oxide, Ti oxide, zirconium oxide, ITO and the like. As the low refractive index layer, silicon oxide is generally used.

As the hard coat layer 162 in the AR layer film (corresponding to 160 in FIG. 3D), DPH is used.
A, polyester acrylate such as A, TMPTA or PETA, or polyfunctional acrylate such as urethane acrylate or epoxy acrylate can be formed by heat curing or curing by ionizing radiation. Here, "having hard performance" or "hard coat" means JI
The pencil hardness test represented by SK5400 indicates a hardness of H or higher. The antifouling layer 164 to be laminated on the AR layer (163 in FIG. 3 (d)) is a water-repellent or oil-repellent coating, and is made of siloic acid-based or fluorine-based antifouling such as fluorinated alkylsilyl compounds. A coating is mentioned.

The electromagnetic wave shielding member produced by laminating the AR layer and being stretched at each position without slack is cut (S210) to form an electromagnetic wave having the layer structure shown in FIG. 3 (d). Obtain a shielding member. (S220)

The thus obtained electromagnetic wave shielding member having the layer structure shown in FIG. 3 (d) is attached to one surface of a transparent base material such as a glass substrate to form the transparent base material. An AR layer film (corresponding to 160 in FIG. 3D) can be attached to the other surface to form an electromagnetic wave shielding plate. As the transparent base material, glass, polyacrylic resin, or polycarbonate resin substrate is preferably used, and a plastic film may be used if necessary. The material of the plastic film includes triacetyl cellulose film, diacetyl cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether. Films, trimethylpentene films, polyetherketone films, (meth) acrylonitrile films and the like can be used, but biaxially stretched polyester is particularly preferable because it is excellent in transparency and durability. Its thickness is usually 8 μm
It is preferably about 1000 μm. It should be noted that a base material having a rigidity of 1 to 10 mm is used for a large-sized display, and an appropriate flexibility with a thickness of 0.1 mm is used for a small display for a character display tube. 01m
A plastic film of m to 0.5 mm is attached to a display and used. The light transmittance of the transparent base material is ideally 100%, but it is preferable to select the light transmittance of 80% or more.

(Modification) Instead of S180 of this example, a flattening resin layer 6 is provided on the uneven surface of the metal mesh portion 5.
On the flattening resin layers 6 and 13, an antireflection layer or
Laminate an antiglare layer. (Figure 7, Figure 8)

(Modification) Instead of S180 of this example, a flattening resin layer 6 is provided on the uneven surface of the metal mesh portion 5.
On this flattening resin layer 6, an adhesive layer containing an absorber (visible light absorber, near infrared absorber) is laminated. (Figure 9)

(Modification) Laminating process S130 of this example
Prior to the above, at least one surface of the metal foil 120 is not blackened, and like the present example, after the etching process (S160) is performed, the surface portion of the metal foil 120 is blackened by a chromate process. As a modified example, a blackening treatment is performed, and thereafter, a laminating treatment of laminating a silicon separator (silicone-treated easily peelable PET film) is performed as in this example. Further, before the cutting process (S210), it is possible to take a form of temporarily winding the film by rolling it up in a roll shape, if necessary. Further, in some cases, a slitting process for making the laminate member 190 a predetermined width can be performed before the masking process (S190). Further, in the present example, the metal foil is a copper foil, but it can be applied to a case where the metal foil is an iron material or the like. In addition, after the lamination of the NIR layer film (S190), a protective film may be attached and cut depending on the case, and another modified example in which this is used as an electromagnetic wave shielding member may be mentioned.

Next, a second example of the embodiment of the method for manufacturing an electromagnetic wave shielding member of the present invention will be described with reference to FIG.
In the second example, instead of the laminated member forming process in the first example, one surface of the metal foil continuous in a strip shape is coated with a resin by a coating method such as extrusion coating or hot melt coating (S135),
This is a laminated member forming process for obtaining a laminated member (S140). As described above, the extrusion coating material includes polyolefin and polyester, and the hot melt coating material includes
Examples thereof include a resin mainly containing ethylene vinyl acetate, a resin mainly containing polyester, and a resin mainly containing polyamide. Except for the laminated member forming process, the process is the same as the first example, and the description thereof is omitted.

Next, a third example of the embodiment of the method for manufacturing an electromagnetic wave shielding member of the present invention will be described with reference to FIG.
Similar to the first example, this example is also a member for producing an electromagnetic wave shielding plate for electromagnetic wave shielding that is placed on the front surface of a display such as a PDP shown in FIG. / Electromagnetic wave shielding by laminating mesh consisting of metal thin film, at least one surface of which is blackened by chromate treatment through an adhesive compounded with polyester polyurethane modified with maleic acid copolymer and aliphatic polyisocyanate With a manufacturing method for mass-producing an electromagnetic wave shielding member having transparency and transparency,
As a metal foil for forming a mesh composed of a metal thin film, a copper foil or iron material (low carbon steel) having a thickness of 1 μm to 100 μm and at least one surface of which is blackened by chromate treatment is used. Is. In this example, similarly to the first example, after performing a laminating process (S180) for laminating a silicon separator (silicone-treated easily peelable PET film), a region corresponding to a region for producing an electromagnetic wave shielding member. Cut each time (S18
5), as the single-wafer state, N of the single-wafer state corresponding to this
The IR layer film and the AR layer film are sequentially laminated with an adhesive layer in between (S195, S205) to produce an electromagnetic wave shielding member (S220). The material of each part and the processing method are the same as those in the first example, and the description thereof will be omitted.

The state of the cutting treatment (S185) of this example (the layer structure corresponding to FIG. 3C) is used as it is as an electromagnetic wave shielding member, and is used alone or in another AR layer film, N.
Transparent base material (glass substrate, etc.) together with IR layer film
It may be attached to the plate and used as an electromagnetic wave shielding plate.

In the first and third examples, the cross section of the characteristic portion in each process up to the laminating process (S180) (the cross section at the P1-P2 position in FIG. 3B) is shown in FIG. A brief description will be given based on. Each drawing of FIG. 2 shows a cross section taken along line P1-P2 of FIG. Incidentally, FIG. 2 shows a lamination process S such as PET film.
It is a figure at the time of using the adhesive agent at 130 hours. By the laminating process (S130 of FIG. 1), the film base 110
The metal foil 120 is disposed on one surface (FIG. 2A) via the adhesive layer 130, as shown in FIG. 2B.
Further, a photosensitive resist is applied on the metal foil 120, dried (FIG. 2 (c)), and then contact-exposed with a predetermined pattern plate, developed, and baked (FIG. 2 (d)). As shown in, a resist pattern 180 having a predetermined shape is formed. Next, the metal foil 120 is etched from one surface using the resist pattern 180 as an etching-resistant mask (FIG. 2E), and further subjected to cleaning treatment, and then an adhesive layer 135 is provided on the surface of the metal foil 120. Silicon separator 140 is laminated via 135. (Fig. 2 (g))

[0055]

EXAMPLES Next, the present invention will be further described with reference to examples. (Example 1) This example is the first example of the embodiment shown in FIG.
Part of the method of manufacturing the electromagnetic wave shielding member of the example is carried out. In the first example of the embodiment shown in FIG. 1,
As a film substrate, a polyethylene terephthalate (also referred to as PET) film having a thickness of 188 μm and a width of 700 mm (A4300 manufactured by Toyobo Co., Ltd.) was coated with the following adhesive 1 by a roll coater and dried to give a coating amount of 4 g / m2
And Adhesive 1 To 100 parts of an ethyl acetate solution of polyester polyurethane modified with a styrene / maleic acid copolymer (manufactured by Rock Paint: solid content (also referred to as NV) 50%),
10 parts of an ethyl acetate solution of an aliphatic polyisocyanate (manufactured by Rock Paint: NV75%) was blended. 45 parts of ethyl acetate was mixed with 100 parts of this mixed solution to prepare an adhesive 1.

As shown in FIG. 12, a copper bump 130 is formed on one side.
Both sides of the copper layer 1200 with 0 attached are blackened by chromate treatment (made by Furukawa Circuit foil, EXP-WS width 700 mm, thickness 9 μm)
Was used as the metal foil. The chromate layer 1100 (blackening layer) on the side of the copper foil 1200 to which the copper bumps 1300 are attached and P
Using a laminating device composed of a metal roll and a rubber roll so that the adhesive surface of the ET film overlaps with each other without wrinkles or bubbles, a laminate member 190 (sheet) having a total thickness of 200 μm was obtained.

Next, a masking process and an etching process are continuously performed from a strip of steel material to form a shadow mask for a cathode ray tube of a color TV on a thin plate (20 μm to 80 μm).
The process from the masking process to the etching process, which is produced by etching from one surface, was performed on an integrated line (hereinafter also referred to as SM line) in which the steel material was stretched.
Laminated member 190 using casein as a photosensitive resist
While being transported, it was applied by pouring so as to cover the entire one surface (metal foil side). As a pattern version,
As shown in FIG. 3 (b), the mesh portion 120A and the grounding frame portion 120B are shaped to form a mesh angle of 30.
Degree, mesh line width 20 μm, mesh pitch (P in FIG. 4
(corresponding to x and Py) having a thickness of 200 μm, contact exposure is carried out in a SM frame baking frame (S153), followed by water development (S154), hardening treatment, etc., and further 100 ° C.
I baked at. (S155)

Then, with the laminating member 190 in a stretched state, a ferric chloride solution at 50 ° C. and 42 ° Baume is used as an etching solution, and the metal foil is exposed by spraying the resist pattern with the resist pattern as an etching resistant mask. The region that is being etched is etched to form a mesh portion and a frame portion for grounding.

Then, on the SM line, in a stretched state,
Washing with water and stripping of the resist were carried out with an alkaline solution, and then washing treatment, drying and the like were performed. The obtained one was used as a test film 1.

Comparative Example 1 A test film 2 was prepared in the same manner as in Example 1 except that the adhesive 1 was changed to the following adhesive 2. Adhesive 2: 100 parts of ethyl acetate solution of polyester polyurethane modified with styrene / maleic acid copolymer (Rock Paint: 50% solid content (NV)) to 100 parts of ethyl acetate solution of aromatic polyisocyanate (Rock Paint (Manufacturing: solid content (NV) 75%) 10 parts were blended. 45 parts of ethyl acetate was mixed with 100 parts of this mixed solution to prepare an adhesive 3.

(Comparative Example 2) A test film 3 was prepared in the same manner as in Example 1 except that the adhesive 1 was changed to the following adhesive 3. Adhesive 3: 100 parts of an ethyl acetate solution of polyester polyurethane (manufactured by Takeda Pharmaceutical Co., Ltd .: solid content (NV) 50%) to 100 parts of an ethyl acetate solution of aliphatic polyisocyanate (Takeda Chemical Industry Co., Ltd .: solid content (NV) 75 %) 10 parts. To 100 parts of this mixed solution, 45 parts of ethyl acetate
Parts to form an adhesive 3.

The optical characteristic results of the test films 1 to 3 are shown in Table 1.
It was shown to. Here, ΔAB * is expressed by the following equation 1. ΔAB * = (Δa * × Δa * + Δb * × Δb *) ^1/2 Equation 1

[0063]

[Table 1]

Here, Δa *, Δb *, Δa * ratio, Δb *
The ratio, ΔAB *, and Tt [%] are expressed as follows in Japanese physical terms. Δa *: L * a * b * Transmission chromaticity difference of color system Δb *: L * a * b * Transmission chromaticity difference of color system Δa * Ratio: Based on Δa * of test film 3 , Ratio of Δa * of each sample Δb * ratio: ratio of Δb * of each sample with reference to Δb * of the test film 3 ΔAB *: chromaticity difference obtained by combining the chromaticity difference between Δa * and Δb * Tt [%]: Total light transmittance

The measuring method of each numerical value shown in Table 1 and the acceptable range of physical properties (excellent etching resistance, optical characteristics, discoloration) are described. Etching resistance: The pattern left by etching does not peel off. About optical characteristics: The concept is that it has high transmittance and is colorless. Here, since Tt is the same, ΔAB * is 4 or less,
Pass 0 or more.

From the results shown in Table 1 and the like above, the electromagnetic wave shielding member adhered with an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and organic polyisocyanate has excellent etching resistance,
It can be seen that the optical characteristics are also excellent. In particular, as in Example 1, the electromagnetic wave shielding member adhered with the adhesive compounded with the aliphatic isocyanate has no discoloration of the adhesive due to etching, excellent etching resistance, and excellent optical characteristics. I understand.

Example 2 The test film 1 was subjected to the following flattening treatment. (Flatization treatment) Using a urethane-based UV curable resin having a viscosity of 1500 mPa · s, a screen is formed only on the uneven surface of the metal foil (mesh portion) so as not to contact the ground electrode portion around the test film 1. Thickness 4 by printing
It was applied to 0 μm. Furthermore, on this screen-printed surface, untreated PET with a high surface smoothness of 38 μm thick
Using the film as a release film with a laminator machine,
Laminated. Then, the untreated PET film having a surface smoothness of 38 μm and having a thickness of 38 μm was cured by curing with an ultraviolet ray having a dose of 200 mj / cm 2, and a flattened metal mesh sheet was manufactured.

[0068]   (Colored adhesive layer)   (Colored adhesive material)   2 parts by weight of nickel complex compound (near infrared ray absorber)   Neodymium oxide (visible light absorber) 2 parts by weight   Polyester resin 550 parts by weight   Methyl ethyl ketone 920 parts by weight   Toluene 920 parts by weight

The colored adhesive material was dispersed and mixed with a three-roll to produce a colored adhesive. Then 100
After applying the colored adhesive to the surface of the flattening layer of the metal mesh sheet subjected to the flattening with a μm applicator, the solvent is dried at about 90 ° C. to give 1
An electromagnetic wave shielding member having a layer structure having a colored adhesive layer of 0 μm was obtained. A glass plate was laminated on the side of the colored adhesive layer of this electromagnetic wave shielding member.

(Spectral transmission and reflectance measurement) Shimadzu
Using spectrometer UV-3100PC, reflectance and transmittance of visible light 380 ~ 780nm, and near infrared 1
The transmittance at 000 nm was measured using an integrating sphere.

(Spectral transmission and reflectance measurement results) Visible light 380-780nm Transmittance (T%) 62% Reflectivity (R%) 15% R / T 0.24 Near infrared 1000nm transmittance (T%) 11%

(Comparative Example 3) The colored adhesive material of Example 2 was changed to the following components. Except for this, the same procedure as in Example 2 was performed. (Colored adhesive material) Polyester resin 550 parts by weight Methyl ethyl ketone 920 parts by weight Toluene 920 parts by weight

The spectral transmission and reflectance measurement results of the obtained electromagnetic wave shielding member were as follows. (Spectral transmission and reflectance measurement results) Visible light 380 to 780 nm transmittance (T%) 77% Reflectance (R%) 38% R / T 0.49 Near infrared 1000 nm transmittance (T%) 92%

[0074]

The electromagnetic wave shielding member of the present invention and the display in which the electromagnetic wave shielding member is directly laminated on the surface of the display have transparency and electromagnetic wave shielding property. Further, not only that, discoloration of the adhesive during mesh processing by etching was eliminated, etching processability was improved, and resistance to mesh processing by etching could be provided. Further, the contrast was improved and the visibility was improved. Furthermore, if necessary, with a layer structure that is as small as possible, it cuts or absorbs near-infrared rays (light) generated from the inside of the display, and among the light emitted from the display panel and the incident external light, in particular, Absorbs a specific wavelength of visible light. As a result, there is no malfunction of other equipment, and good visibility is obtained by improving the contrast of the image on the display screen. By using a mesh made of a copper thin film, it is particularly suitable for etching processing and also has a high electromagnetic wave shielding effect. By subjecting the mesh made of a metal thin film to chromate treatment, and in particular, by setting the black density thereof to 0.6 or more, the performance of absorbing external light is particularly enhanced, and the visibility becomes higher.

[Brief description of drawings]

FIG. 1 is a manufacturing process flow chart showing an embodiment of a method for manufacturing an electromagnetic wave shielding member of the present invention.

[Figure 2] Masking treatment, etching treatment, silicon
Partial cross-sectional view for explaining a laminating process for laminating a separator (silicone-treated easily peelable PET film)

FIG. 3 (a) is a diagram showing a positional relationship between a mesh portion and a grounding frame portion of an electromagnetic wave shielding member formed with a laminate member, and FIG. 3 (b) is a mesh portion and a grounding frame. 3C and FIG. 3D are cross-sectional views showing the layer structure of the electromagnetic wave shielding member to be produced.

FIG. 4 is a diagram for explaining an electromagnetic wave shielding member.

FIG. 5 is a diagram for explaining a usage pattern of an electromagnetic wave shielding plate.

FIG. 6 shows two examples of the layer structure of the metal foil 120 shown in FIG.
Sectional views shown in FIGS. 6A and 6B.

FIG. 7 is a cross-sectional view showing an example of the layer structure of an electromagnetic wave shielding member of the present invention.

FIG. 8 is a cross-sectional view showing another example of the layer structure of the electromagnetic wave shielding member of the present invention.

FIG. 9 is a schematic cross-sectional view showing an example of a display in which the electromagnetic wave shielding member of the present invention is laminated.

FIG. 10 is a perspective view showing an example of a layer structure of an electromagnetic wave shielding member of the present invention. (Example 1)

11 is a schematic diagram of the electromagnetic wave shielding member 4000 of FIG.
It is a sectional view showing an example of a vertical section layer composition at the time of being cut by a plane parallel to a 000 mesh. (Example 1)

12 is a schematic cross-sectional view showing a state before etching of the copper foil 1000 to which a copper bump 1300 constituting the electromagnetic wave shielding member 4000 of FIG. 11 is attached.

[Explanation of symbols]

1 Antireflection Layer and / or Antiglare Layer 2 Glass or Acrylic Transparent Substrate 3 Adhesive or Adhesive 4 Transparent Film Substrate 5 Mesh Made of Metal Thin Film 6 Flattening Layer 7 Antireflection Layer and / or Antiglare Layer 8 Visible Absorber that absorbs a specific wavelength of light and / or near infrared light 9 Adhesive 10 Electromagnetic wave shielding member 12 Adhesive or pressure sensitive adhesive 13 Flattening layer 14 Adhesive or pressure sensitive adhesive 15 Display 20 Electromagnetic wave shielding member 30 Electromagnetic wave shielding Display 110 with a member for metal film 120 Metal foil 121 Metal layer 122 Chromate layer (blackening layer) 120A Mesh part 120B Grounding frame 120C Processing part 130 Adhesive layer 135 Adhesive layer 140 Silicon separator (protective film ) 150 NIR layer film 151 Film 152 NIR layer 160 AR layer film 161 Film 16 Hard coat layer 163 Antireflection layer 164 Antifouling layer 170, 175 Adhesive layer 190 Laminating member (laminating member) 400 Electromagnetic wave shielding plate 410 Mesh portion 415 Grounding frame portion 417 Metal thin film 430 Transparent base material 450, 470 line 1000 Copper Foil 1100 Chromate (treatment) layer 1200 Copper layer 1300 Copper bump 2000 Adhesive layer 3000 Polyethylene terephthalate film 4000 Electromagnetic wave shielding member

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 5E321 AA04 BB21 BB41 BB53 CC16                       GG05 GH01                 5G435 AA00 AA01 AA02 AA16 GG11                       GG33 HH02 HH03 KK07

Claims (9)

[Claims] 1. An electromagnetic wave in which a mesh made of a metal foil is laminated on one surface of a transparent film substrate through an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. Shielding member. 2. The electromagnetic wave shielding member according to claim 1, wherein the transparent film base material is polyethylene terephthalate, and the metal foil has a thickness of 5 μm to 20 μm. 3. The metal foil according to claim 1 or 2, wherein the metal foil is a copper foil, and at least one surface of the metal foil is subjected to a roughening treatment by attaching a copper bump by cathodic electrodeposition, An electromagnetic wave shielding member, characterized in that at least one surface of the metal foil is subjected to anticorrosive chromate treatment. 4. An electromagnetic wave shielding member, characterized in that a transparent film base material is adhered to a surface of the copper foil of claim 3 to which copper bumps due to cathodic electrodeposition are adhered. 5. A transparent film substrate is laminated with an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate, and the metal foil of the laminated member is etched. A method for manufacturing an electromagnetic wave shielding member, which is obtained by forming a mesh. 6. The method for manufacturing an electromagnetic wave shielding member according to claim 5, wherein ferric chloride is used as an etching solution. 7. A styrene / maleic acid copolymer, wherein a transparent film substrate has a mesh formed of a metal thin film and an absorbent for absorbing a specific wavelength of visible light and / or near infrared is contained on one surface of the transparent film substrate. A member for electromagnetic wave shielding, which is laminated via an adhesive containing a polymer-modified polyester polyurethane and an aliphatic polyisocyanate. 8. A transparent film substrate is laminated on one surface with a mesh consisting of a metal thin film via an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. In an electromagnetic wave shielding member in which a layer for flattening the uneven surface of a mesh made of a metal thin film is laminated, at least one of the flattening layer and the adhesive absorbs a specific wavelength of visible light and / or near infrared light. An electromagnetic wave shielding member containing an absorber. 9. A transparent film substrate is laminated on one surface with a mesh composed of a metal thin film via an adhesive containing a polyester polyurethane modified with a styrene / maleic acid copolymer and an aliphatic polyisocyanate. In the electromagnetic wave shielding member in which a layer for flattening the uneven surface of the mesh made of a metal thin film is laminated, the flattening layer, or
In an electromagnetic wave shielding member in which an adhesive or a pressure-sensitive adhesive is laminated on at least one surface of a transparent film substrate, at least one of the flattening layer, the adhesive or the pressure-sensitive adhesive specifies visible light and / or near infrared. An electromagnetic wave shielding member containing an absorber that absorbs the wavelength of.