JP2003103696A - Plate for forming irregularity, its manufacturing method, electromagnetic wave shielding material using the same, its manufacturing method, and electromagnetic wave shielding component and electromagnetic wave shield display which use the electromagnetic wave shielding component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electromagnetic wave shielding material of a good productivity which achieves sufficiently functions of the electromagnetic wave shielding material such as an electromagnetic wave shielding property, a transparency, a nonvisibility and the like, and to provide a plate useful therefor and its manufacturing method. SOLUTION: A plate for forming an irregularity is manufactured by drawing a geometrical figure by etching an etching layer of a laminated body in which a carrier layer, a barrier layer and the etching layer are successively laminated. Thereafter, a process for transferring the geometrical figure to at least one side surface of a resin substrate and a process for filling up a conductive material in a depressed part formed on the resin substrate are contained to provide the method for manufacturing electromagnetic wave shielding material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate for forming irregularities used for producing a resin film having irregularities, a resin plate having irregularities, a method for producing the same, an electromagnetic wave shielding material using the same, and production thereof. The present invention relates to a method, an electromagnetic wave shielding structure using the electromagnetic wave shielding material, and an electromagnetic wave shield display. The electromagnetic wave shielding material and the electromagnetic wave shielding structure include CRT, PDP (plasma), liquid crystal,
It has a function of shielding an electromagnetic wave generated from the surface of a display such as an EL.

[0002]

2. Description of the Related Art In recent years, as the use of various electric equipments and electronic equipments has increased, electromagnetic noise interference has also increased. As a measure against radiated noise, it is necessary to electrically insulate the space, so the housing should be a metal body or a high conductive material, a metal plate should be inserted between the circuit boards, and the cable should be a metal foil. The method of wrapping is adopted. These methods can be expected to have an electromagnetic wave shielding effect on circuits and power supply blocks.
Since it is opaque, it cannot be applied as an electromagnetic wave shield that is generated from the surface of a display such as a PDP.

As a method for achieving both the electromagnetic wave shielding property and the transparency, 1) a method of forming a thin film conductive layer by vapor-depositing a metal or a metal oxide on a transparent substrate (JP-A-1-278).
Japanese Unexamined Patent Publication No. 800 and Japanese Unexamined Patent Publication No. 5-323101) have been proposed. On the other hand, 2) an electromagnetic wave shielding material in which a good conductive fiber is embedded in a transparent base material (Japanese Patent Application Laid-Open No. 5-327274).
JP-A-5-269912) and 3) an electromagnetic wave shield material obtained by directly printing a conductive resin containing a metal powder or the like on a transparent substrate (JP-A-62-57297).
JP-A-2-52499), and further, 4) forming a transparent resin layer on a transparent substrate such as polycarbonate having a thickness of about 2 mm, and forming a copper plating layer thereon by an electroless plating method. Then, an electromagnetic wave shielding material in which a mesh pattern is formed by a photolithographic method (see Japanese Patent Laid-Open No. 5-283889), and 5) A method of directly forming a mesh pattern on a metal foil-coated substrate by using a photolithographic method (See Japanese Patent Laid-Open No. 9-024575) has been proposed.

However, in the above method 1), when the film thickness is such that transparency can be achieved (10 Å for metal, 1,000 to 2,000 Å for metal oxide), the surface resistance of the conductive layer increases. Too much, so 30MHz-1GHz
20 for the shield effect of 30 dB or more required by
The value was not more than dB, which was insufficient. The electromagnetic wave shielding material of 2) above has a sufficiently large electromagnetic wave shielding effect of 40 to 50 dB at 30 MHz to 1 GHz, but the fiber diameter necessary for regularly disposing the conductive fibers so as to prevent electromagnetic wave leakage is too thick as 30 μm or more. Therefore, the fibers were not visible (hereinafter referred to as visibility) and were not suitable for display applications. Similarly, in the case of the electromagnetic wave shielding material of 3) above, the line width is 50 μm due to the limit of printing accuracy.
As described above, it is not suitable because visibility is exhibited.

On the other hand, in the case of the above electromagnetic wave shielding material 4), it is necessary to roughen the surface of the transparent substrate in order to secure the adhesion of electroless plating. As the roughening means, generally, a highly toxic oxidizing agent such as chromic acid or permanganic acid must be used, and it is difficult for this method to perform satisfactory roughening with a resin other than ABS. Further, even if the electromagnetic wave shielding property and the transparency can be achieved by this method, it is difficult to reduce the thickness of the transparent substrate and it is not suitable as a film forming method. Furthermore, if the transparent substrate is thick, it cannot be closely attached to the display, and electromagnetic waves leak from there. In terms of manufacturing, there are also drawbacks that the shield material is bulky because it cannot be made into a scroll or the like, and the manufacturing cost is high because it is not suitable for automation. Furthermore, 5) above
In the method using photolithography, there are many steps,
There is a problem that it is not good at microfabrication, and the line width is limited to ten and several μm.

In addition to electromagnetic wave shielding materials, there is a demand for a highly productive manufacturing method for resin films, resin plates and the like having irregularities on the surfaces of polishing pads, reflection films and the like.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and sufficiently fulfills the function as an electromagnetic wave shielding material such as electromagnetic wave shielding property, transparency, non-visibility and the like, and further, the productivity is improved. The present invention provides a method for producing a good electromagnetic wave shielding material, and also provides a useful plate and a production method therefor. The present invention also provides an electromagnetic wave shielding structure and an electromagnetic wave shield display using the above electromagnetic wave shielding material. Further, the above-mentioned plate provides not only the production of an electromagnetic wave shielding material, but also a plate useful for a resin film, a resin plate or the like having irregularities on the surface of a polishing pad, a reflective film or the like.

[0008]

The present invention relates to the following. 1. A method for manufacturing a plate for forming irregularities, characterized by drawing a geometrical figure by etching an etching layer of a laminate in which a carrier layer, a barrier layer and an etching layer are sequentially laminated. 2. A laminated body in which a carrier layer, a barrier layer, and an etching layer are sequentially laminated is a carrier layer of JIS K 71.
04 R _Z forms a barrier layer on the surface of the surface roughness is 0.01 to 0.1 m, further, the manufacturing method of the plate on the claim 1, wherein those which are produced by forming an etching layer thereof . 3. Item 3. The method for producing a plate according to Item 1 or 2, wherein the barrier layer is a layer that is not substantially etched by etching the etching layer. 4. Item 4. The method for producing a plate according to any one of Items 1 to 3, wherein the material of the etching layer is copper and the material of the barrier layer is nickel or a nickel alloy. 5. Item 5. The method for producing a plate according to Items 1 to 4, wherein the etching is performed by a photolithography method using an alkali etchant. 6. Item 6. The method for producing a plate according to any one of Items 1 to 5, wherein the carrier layer is made of copper foil. 7. 7. The method for producing a plate according to items 1 to 6, wherein the carrier layer is made of a copper foil whose surface in contact with the barrier layer is polished. 8. Item 9. A plate for forming unevenness produced by the method according to any one of Items 1 to 7. 9. A plate for forming unevenness in which a layer for drawing a geometrical figure is formed on the barrier layer. 10. Item 9 further having a carrier layer below the barrier layer
The listed version. 11. The surface of the carrier layer that contacts the barrier layer is JIS
Edition claim 10, wherein R _Z of K 7104 has a surface roughness is 0.01 to 0.1 m. 12. The plate according to claim 9, wherein the material of the layer forming the geometrical figure is an etchable layer, and the barrier layer is a layer which is not substantially etched by this etching. 13. Item 1 in which the material of the layer forming the geometrical figure is copper and the material of the barrier layer is nickel or nickel alloy
Edition of 2. 14. Line width of geometric figures is 0.1 μm or more and 50 μm
Item 9 below, in which the line spacing is 10 μm or more
The plate according to any one of 13 above. 15. Item 15. The plate according to Item 14, wherein the depth of the recesses is 0.1 μm or more. 16. A step of transferring the geometrical figure of the plate according to any one of claims 8 to 15 to at least one surface of a resin base material, and a step of filling a conductive material in a recess formed in the resin base material. And a method for producing an electromagnetic wave shielding material. 17. Conductive material has a specific resistance value of 1.0 × 10 ^-4 Ω
Item 17. The method for producing an electromagnetic wave shield material according to Item 16, which has a size of cm or less. 18. Item 18. The method for producing an electromagnetic wave shielding material according to any one of Items 16 to 17, wherein the conductive material is a conductive paste, or the conductive paste is metal-plated. 19. Item 19. The method for producing an electromagnetic wave shield material according to any one of Items 16 to 18, wherein the conductive paste is a silver paste, a copper paste, a nickel paste, or a gold paste. 20. Item 20. The method for producing an electromagnetic wave shield material according to any one of Items 18 to 19, wherein the conductive paste is a paste that is cured by heat or radiation. 21. Item 21. The method for producing an electromagnetic wave shield material according to any one of Items 16 to 20, wherein the conductive material embedded in the recess of the resin substrate is electrically connected as a whole. 22. Item 22. The method for producing an electromagnetic wave shield material according to any one of Items 16 to 21, wherein the resin base material contains at least one of a radiation-curable resin, a thermosetting resin, and a thermoplastic resin. 23. Item 16. An electromagnetic wave shielding material produced by the method according to any one of items 16 to 22. 24. 24. An electromagnetic wave shielding structure comprising the transparent supporting substrate and the electromagnetic wave shielding material according to item 23 laminated on at least one surface thereof. 25. Item 24. An electromagnetic wave shield display characterized in that the electromagnetic wave shield material according to item 23 is attached to a display surface. 26. Item 24. An electromagnetic wave shield display in which the electromagnetic wave shield structure according to Item 24 is attached to a display.

[0009]

DETAILED DESCRIPTION OF THE INVENTION

First, a laminated body in which a carrier layer, a barrier layer and an etching layer are laminated in order will be described.
The etching layer is a layer that can be etched by a photolithography method or the like. The barrier layer is made of a metal material of the metal layer having a corrosion resistance to the etching liquid of the etching layer. The carrier layer may have a function of supporting the barrier layer thereon. As a material, the etching layer is preferably an etchable metal layer such as copper. When the etching layer is copper, the barrier layer is preferably a metal layer of nickel, nickel-phosphorus alloy, nickel-tin alloy, nickel-iron alloy, lead, tin-lead alloy, or the like. The thickness of the metal layer as the etching layer is preferably 0.5 to 20 μm, more preferably 1 μm or more, and further preferably 15 μm or less from the viewpoint of precision etching property. The thickness of the metal layer as the barrier layer is 0.01
It is preferable that it is in the range of
More preferably, it is within the range of m. 0.01μ
When it is less than m, the corrosion resistance of the etching layer to the etching solution is lowered, and when it exceeds 3 μm, it becomes excessive to serve as a barrier layer, and it takes time to form the barrier layer.
It may take too long to etch the core and damage the underlying copper layer.

As the carrier layer, a plastic base material such as polyethylene terephthalate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, triacetyl cellulose, methyl methacrylate or the like can be used, and copper, silver, nickel, gold can be used. A metal plate or foil of aluminum, stainless steel, or the like can be used. The carrier layer is a metal foil having sufficient strength, that is, a thickness of 5
A metal foil of ˜300 μm is preferred. The thickness of the metal foil as the carrier layer is more preferably 12 μm or more from the viewpoint of strength, and further preferably 150 μm or less from the viewpoint of removability. As the carrier layer, copper foil is easy to use, and is particularly preferable from the viewpoint of availability of materials.

[0012] In the laminate, a step of forming the above-mentioned metal layer on at least one surface of a carrier layer by a method such as electrolytic or electroless plating, and further etching on the surface by a method such as electrolytic or electroless plating. It can be manufactured by forming a metal layer to be a layer.

When the step of filling the conductive material into the concave portion of the resin base material having a smooth convex surface, the conductive material is hard to adhere to the convex surface of the resin base material, and the unnecessary conductive material is used. The process of removing is easy. In order to enhance the smoothness of the convex surface of the resin base material, it is preferable because it is easy and easy to enhance the surface smoothness of the concave bottom surface in the plate for forming the irregularities whose shape is transferred to the resin base material. In order to improve the smoothness of the surface of the recess in the above plate, in the above method for producing a plate, the surface smoothness of a plastic substrate as a substrate, a metal plate or foil polished to a mirror surface state, etc. was excellent. A substrate may be used. The smoothness of the surface of the concave portion of the plate for forming the uneven portion is such that R _{Z of} JIS K 7104 is 0.1 μm.
m or less is preferable, and 0.01 to 0.1 μm is more preferable. Further, the surface of the concave portion of the plate for forming the uneven portion has R _max of 0.2 μm or less and _Ra of 0.05.
It is preferably μm or less. The lower limit of R _max is not particularly limited, but is usually 0.05 μm. Also, R
The lower limit of _a is not particularly limited, but is usually 0.005. In the above, the measurement distance according to JIS K 7104 is 8 mm.

As a method of producing a plate, a metal plate or foil (barrier layer) is electrolytically or electrolessly plated with another kind of metal (etching layer) to a desired thickness on the metal plate or foil. There is a method of forming a convex or concave geometrical figure by etching the metal of the other type in a process using a photolithography by further forming a mask pattern on the above-described metal pattern. In addition, as a chemical solution used when processing in the process using photolithography, from the viewpoint of maintaining the smoothness of the surface, it is formed by electrolytic plating or electroless plating without attacking the metal whose surface is mirror-polished. It is preferable that it only corrodes the removed metal. Specifically, for example, after polishing the nickel or nickel alloy layer to a mirror surface state, copper plating is performed,
When the copper is processed with the alkaline etchant, only the copper is processed and the nickel layer is not attacked. Therefore, a plate for forming a concave portion having a convex geometric figure without losing the surface smoothness of the nickel layer. Can be manufactured. The thickness of the barrier layer is as described above. Further, the thickness of the metal layer (etching layer) formed on the metal plate or foil is also
As described above. For the production of the plate for forming the unevenness, it is simple and preferable to etch the etching layer of the laminate in which the carrier layer, the barrier layer and the etching layer are sequentially laminated by a method such as a photolithography method.

The etchant used for the above-mentioned etching is selected according to the material of the metal layer. When the etching layer is a copper layer, the etchant is a solution containing chlorine ions, ammonium ions and copper ions (specifically, Is an aqueous solution containing 100 to 200 g / liter of copper chloride, 100 to 200 g / liter of ammonium hydroxide and 200 to 300 g / liter of ammonium chloride), and 100 g / liter of ammonium persulfate.
Aqueous solution containing liter and ammonium chloride 100-300 g / liter, ammonium hydroxide 200-300
An aqueous solution containing g / liter and hydrogen peroxide of 50 to 300 g / liter (hereinafter referred to as "alkali etchant") is used. An acidic etchant can also be used.

The plate for forming the irregularities thus formed is preferably used by being wound around a roll in order to produce a transparent resin base material having continuous recesses. Further, by performing the same processing as above on the metal roll, it is also possible to continuously manufacture a transparent resin base material having a seamless uneven portion.

In the electromagnetic wave shielding material of the present invention, it is preferable that the concave portion of the resin base material forms a geometrical figure.
It is preferable that the line width of the geometric pattern is 0.1 μm or more and 50 μm or less and the line width is 10 μm or more. Further, the depth of the concave portion on the resin substrate is preferably 0.1 μm or more. As described above, the line width of the geometric figure is extremely small and the line interval is sufficiently large, so that the electromagnetic wave shield excellent in transparency and invisibility can be realized. Further, the line spacing of the geometrical figure can be set to be sufficiently smaller than the wavelength of the electromagnetic wave to be shielded, so that excellent shielding property is exhibited.

The resin substrate preferably contains at least one of a radiation-curable resin (hereinafter referred to as "radiation-curable resin"), a thermosetting resin, and a thermoplastic resin. A curable resin is preferably used because it can form a recess having a more accurate shape. Above all, a radiation curable resin is more preferably used because it is high or short. Here, the radiation refers to actinic radiation such as ultraviolet rays, far infrared rays, infrared rays, X-rays, and electron beams (that is,
Radiation capable of activating the resin by directly acting on the resin to cure the resin, or radiation capable of activating the photosensitizer or photocatalyst), especially with ultraviolet rays or electron beams. Preferably there is. The resin used is preferably one whose fluidity can be controlled in a relatively short time. For example, a resin that flows when a plate (mold) for forming a recess is applied and then hardens in a short time is preferable. From this point of view, a radiation curable resin, a thermoplastic resin, and a thermosetting resin are preferably used in this order. Further, it is preferable that the formed recess has good heat stability, and in this respect, a radiation-curable resin, a thermosetting resin, or a thermoplastic resin is preferably used in this order.

The specific resistance value of the conductive material is 1.0 × 10 ^-4
It is preferably Ω · cm or less. This is because the skin depth of the conductive material is reduced, so that the depth of the recess can be suppressed within an appropriate range. In addition, the conductive material is
It is preferable that the conductive paste is used, or the conductive paste is plated with metal. The conductive metal used for the conductive paste or the plating metal applied on the conductive paste is preferably silver, copper, nickel or gold. This is because these are excellent in conductivity, resin dispersibility, processability, and resin adhesion. In addition, the conductive paste is preferably a paste that is cured by heat or radiation from the viewpoint that the change in conductivity with time is small. The conductive materials filling the recesses are preferably electrically connected to each other. This is because it can be easily connected to an external electrode for grounding when attached to a display or the like.

The resin base material may be a resin layer laminated on a substrate made of transparent plastic or glass. In that case, the transparent plastic is preferably selected from polyethylene terephthalate, polyethylene, polypropylene, polyimide, polymethylmethacrylate, triacetylcellulose or polycarbonate. This makes it possible to obtain an electromagnetic shielding material which is inexpensive, excellent in transparency and heat resistance, and easy to handle.
The transparent plastic can be used in the form of a film or a plate, and in particular, it is easy to follow the irregularities of the adherend such as a display, so that it has excellent adhesion and can prevent electromagnetic wave leakage from a gap between the adherend and the like. From the viewpoint, a flexible film is preferably used. As the resin layer laminated on this substrate, it is preferable to use a resin layer containing at least one of a radiation-curable resin, a thermosetting resin, and a thermoplastic resin, like the resin base material. it can.

Next, the method for producing an electromagnetic wave shield material according to the present invention includes the steps of forming a recess on at least one surface of the resin base material and the step of filling the formed recess with a conductive material. It is a feature. Further, when the conductive material adheres to the part other than the recess, it is preferable to include a step of removing the conductive material adhered to the part other than the recess. According to the manufacturing method of the present invention,
Transparency (visible light transmittance) is possible because it is possible to easily perform ultra-fine wiring processing with high accuracy by, for example, curing the base resin while forming the recess using a plate (mold).
It is possible to manufacture an electromagnetic wave shield material having good non-visibility.

Further, the electromagnetic wave shielding structure according to the present invention is
It is characterized by comprising a transparent supporting substrate and the electromagnetic wave shielding material of the present invention laminated on at least one surface of the transparent supporting substrate. A plastic plate or a glass plate is preferably used as the transparent support substrate. By stacking the electromagnetic wave shielding material of the present invention, the shield body is excellent in transparency and visibility, has little warpage, and is lightweight and compact.

Furthermore, the electromagnetic wave shield display according to the present invention is characterized in that the electromagnetic wave shield material or the electromagnetic wave shield structure of the present invention is attached to the display surface. As described above, since the electromagnetic wave shield display of the present invention has the large visible light transmittance, good non-visibility, and small electromagnetic wave leakage, the electromagnetic wave shield material or the electromagnetic wave shield structure of the present invention is attached to the display surface. Therefore, a clear image can be comfortably viewed under almost the same conditions as in a normal state without increasing the brightness of the.

Next, with reference to the drawings, an electromagnetic wave shielding material, a method for manufacturing the same, an electromagnetic wave shielding structure and an electromagnetic wave shield display according to the present invention will be described in detail according to embodiments of the present invention.

As the resin base material of the present invention, a material containing at least one of radiation curable resin, thermosetting resin and thermoplastic resin can be preferably used. Here, since the resin base material contains at least one of the above resins, two or more kinds may be mixed by blending or copolymerization. It may be composed of any composition containing one or more of these resins. The combination of resins may be radiation-curable resins, thermosetting resins, or thermoplastic resins, or any combination of these three resins (one or more thermosetting resins and 1 One or more thermoplastic resins, one or more radiation curable resins and one or more thermoplastic resins).

FIG. 1 is a sectional view schematically showing an example of the resin base material of the present invention. The resin base material (1) having the recesses (13) may be formed of only a resin layer as shown in FIG. 1 (a), or a transparent plastic (plastic film) as shown in FIG. 2 (b). Alternatively, a plastic plate) or a substrate made of glass (base film; 1)
The resin layer (11) may be laminated on 2). Although not shown in the drawing, the recesses (13) may be formed on both sides of the resin base material. Resin base material (1)
Can be preferably used as a film formed by an ordinary method, and can be an electromagnetic wave shield material having excellent adhesion to an adherend and capable of preventing electromagnetic wave leakage.

The type of resin (polymer) is
Natural rubber, polyisoprene, poly-1,2-butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-2-t-butyl-1,3
-(Di), such as butadiene, poly-1,3-butadiene
Enes, polyoxyethylene, polyoxypropylene,
Polyethers such as polyvinyl ethyl ether, polyvinyl hexyl ether, polyvinyl butyl ether,
Polyesters such as polyvinyl acetate and polyvinyl propionate, polyurethane, ethyl cellulose,
Polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, polysulfide, phenoxy resin, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, poly-
t-butyl acrylate, poly-3-ethoxypropyl acrylate, polyoxycarbonyltetramethylene,
Polymethyl acrylate, polyisopropyl methacrylate, polydodecyl methacrylate, polytetradecyl methacrylate, poly-n-propyl methacrylate,
Poly-3,3,5-trimethylcyclohexyl methacrylate, polyethyl methacrylate, poly-2-nitro-2-methylpropyl methacrylate, poly-1,1-
Examples thereof include thermoplastic resins such as poly (meth) acrylic acid esters such as diethyl propyl methacrylate and polymethyl methacrylate, and thermosetting resins such as phenol resins, melamine resins, epoxy resins, xylene resins, urethane resins and alkyd resins.

Further, as the resin which is hardened by the actinic radiation such as ultraviolet rays and electron rays used in the present invention, acrylic resin, epoxy resin, polyester resin, urethane resin and the like are used as base polymers, each of which is radically polymerizable or Examples of radically polymerizable functional groups that can be exemplified by materials having a cationically polymerizable functional group are groups having a carbon-carbon double bond such as an acrylic group (acryloyl group), a methacryl group (methacryloyl group), a vinyl group and an allyl group. Therefore, an acrylic group (acryloyl group) having a good group life is preferably used.

As the cationically polymerizable functional group, an epoxy group (glycidyl ether group, glycidyl amine group) is typical, and a highly reactive alicyclic epoxy group is preferably used. Specific materials include acrylic urethane, epoxy (meth) acrylate, epoxy modified polybutadiene, epoxy modified polyester, polybutadiene (meth) acrylate, acrylic modified polyester and the like. When the actinic radiation is ultraviolet rays, as the photosensitizer or photoinitiator added during ultraviolet curing, known materials such as benzophenone-based, anthraquinone-based, benzoin-based, sulfonium salts, diazonium salts, onium salts, and halonium salts can be used. Can be used.

The above resins may be used alone or in a blend of two or more kinds. Moreover, you may use the copolymer which copolymerized these 2 or more types as needed, such as acrylic resin. For example, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, etc. can be used as the copolymer resin of acrylic resin and other than acrylic. Particularly, as shown in FIG. 1B, the resin layer (11) of the resin base material (1) having a structure in which the resin layer (11) is laminated on the substrate (12) has a point of adhesion to the substrate (12). Therefore, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent as copolymer resins for acrylic resins. As epoxy acrylate,
1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane tri Glycidyl ether, glycerin triglycidyl ether,
Examples thereof include (meth) acrylic acid adducts such as pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether. A polymer having a polar group in the molecule such as epoxy acrylate is used as a substrate (12).
Useful for improving adhesion to Two or more kinds of these copolymer resins can be used in combination, if necessary.

These resin base materials (1) or resin layers (1
The softening temperature of the polymer of 1) is 200 because of the handling property.
C. or less is preferable, and 150.degree. C. or less is more preferable. When the environment used is 80 ° C or lower, the softening temperature of the resin layer is
From the workability, 80 to 120 ° C is most preferable. On the other hand, the weight average molecular weight of the polymer which is the main component of the resin substrate (1) or the resin layer (11) (measured using a calibration curve of standard polystyrene by gel permeation chromatography, the same applies hereinafter) is From the viewpoint of securing the adhesion to the substrate (12) by the cohesive force, it is preferable to use one having 300 or more.

The resin substrate (1) or the resin layer (1
1) is an additive such as a diluent, a plasticizer, an antioxidant, a filler, a colorant, a surfactant, an ultraviolet absorber or a tackifier, if necessary, to one or more kinds of the above polymers. It may be formed using the compounded composition. Also,
When the resin base material (1) or the resin layer (11) is used in the form of a film, a small amount of filler is added to improve the film forming processability to give unevenness to the film surface, thereby making The film may be slippery and the winding property may be improved. The thickness of the resin layer is 1 to
The thickness can be 1,000 μm, preferably 10 to 100 μm.

As the above (12), a plastic plate,
Although it may be a glass plate or the like, a flexible plate is preferable, and for example, a plastic film is preferably used. Examples of transparent plastics for plastic films or plastic plates include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, polystyrene and ethylene-vinyl acetate copolymer,
Vinyl-based resins such as polyvinyl chloride and polyvinylidene chloride, polysulfones, polyether sulfones, polycarbonates, polyamides, polyimides, acrylic resins, polyacetyl cellulose and the like can be used. Among these plastics, it is preferable to use a film made of polyethylene terephthalate, polyethylene, polypropylene, polyimide, polymethylmethacrylate, triacetyl cellulose or polycarbonate from the viewpoint of transparency, heat resistance, handleability, and price, and polyethylene terephthalate film or It is more preferable to use a polycarbonate film. The film for these substrates may contain a small amount of filler for the same reason as above. Further, the surface of the film may be subjected to a roughening treatment such as matting for improving the adhesiveness to the resin substrate.

The resin layer (11) may be formed on the substrate (12) by applying a resin or a resin composition on the base material and integrating them in accordance with a usual method. When the resin composition is a radiation-polymerizable resin composition containing an organic solvent,
After printing and drying the resin composition on the substrate with a screen printing machine,
Alternatively, after coating and drying with a roll coater, the resin can be polymerized and cured by irradiating with actinic radiation such as ultraviolet rays, far infrared rays, infrared rays or X-rays and electron beams, and further heating if necessary. In the case of a radiation-polymerizable resin containing no organic solvent, the drying step can be omitted.
On the other hand, when the resin composition is a thermosetting resin composition,
The resin composition may be printed or applied on a substrate, dried if necessary, and then heated at a temperature at which curing occurs. In addition, the resin layer (11) formed in a film shape is formed on the substrate (1
It may be laminated on 2) and pressed and integrated. Alternatively, the two may be bonded together using an adhesive (described later) (the adhesive layer is not shown in the drawing).

The resin base material (1) or the resin layer (11) is
It may be a single layer body or a multilayer body, and it is preferable that the total visible light transmittance is 70% or more and the thickness is 1 mm or less. Further, the thickness of each of them is preferably 1 to 1000 μm, and more preferably about 10 to 200 μm. The thickness of the equipment (12) is preferably 5 to 500 μm, and more preferably 10 to 200 μm, from the viewpoint of handling convenience and ensuring the transmittance of visible light.

The above (13) is preferably formed on the surface of the resin base material so as to draw a geometrical figure. Geometric figures include equilateral triangles, isosceles triangles, right triangles and other triangles, squares, rectangles, rhombuses, parallelograms, trapezoids and other quadrilaterals, (regular) hexagons, (regular) octagons, and (regular) dozens. It is a pattern that combines squares, (regular) n-gons such as (regular) decagons (n is a positive integer), circles, ellipses, star shapes, etc.
These units can be used alone or in combination of two or more. From the viewpoint of electromagnetic wave shielding properties, a triangle is most effective, but from the viewpoint of visible light transmission, the aperture ratio increases as the number of (positive) n-gons increases with the same line width. When the electromagnetic wave shielding material of the present invention is used on the surface of a display or the like, the aperture ratio is preferably 50% or more, more preferably 60% or more from the viewpoint of visible light transmittance. Here, the aperture ratio is the percentage of the ratio of the area obtained by subtracting the area of the conductive material of the geometric pattern drawn with the conductive material from the effective area to the effective area of the electromagnetic wave shielding material. When the area of the display screen is taken as the effective area of the electromagnetic wave shielding material, it is the ratio at which the screen can be seen.

The line width of the geometrical figure is 0.1 μm.
It is preferably 50 μm or more and 50 μm or less. The line width is
If electrically conductive with each other, it is preferable to be thin from the viewpoint of visible light transmissivity, but if it is too thin, formation of recesses and embedding of a conductive material, especially embedding tends to be difficult, More preferably, it is 1 μm or more. On the other hand, the line width is more preferably less than 30 μm, further preferably 25 μm or less, from the viewpoint of non-visibility of the geometrical figure. Further, the line interval is preferably 10 μm or more because the larger the line interval, the higher the aperture ratio and the visible light transmittance. Here, when the line spacing becomes complicated due to a combination of geometrical figures and the like, the area is converted into a square area based on the repeating unit, and the length of one side thereof is taken as the line spacing. On the other hand, if the line spacing becomes too large, the electromagnetic wave shielding property deteriorates, so the line width is preferably 1000 μm (1 mm) or less.

The depth (line thickness) of the recesses on the resin substrate is preferably 0.1 μm or more, and more preferably 1 μm or more from the viewpoint of electromagnetic wave shielding properties. Further, from the viewpoint of visible light transmittance, the line interval is 120 μm.
More preferably, the line thickness is 18 μm or less and the line thickness is 18 μm or less. The cross-sectional shape of the recess is not particularly limited, and may be any shape such as a triangle, a semicircle, an ellipse, etc., as well as the illustrated square. Furthermore, in order to make the electromagnetic wave shielding property sufficient, whether the conductive material filling the recess forms a small closed curve (for example, the geometrical figure described above), and whether the closed curves share some lines with each other. Alternatively, recesses may be provided such that they are connected and each closed curve is sized to fit within a circle of a size less than or equal to the wavelength of the electromagnetic wave to be shielded.

Next, as the conductive material in the present invention, a conductive paste in which a conductive metal is dispersed in a resin can be preferably used. The specific resistance value required for the conductive material is preferably 1.0 × 10 ⁻⁴ Ω · cm or less, and more preferably 5.0 × 10 ⁻⁵ Ω · cm or less. It is preferable that when the concave portion is filled with the conductive material, the geometrical figure drawn with the conductive material is electrically conductive. Examples of the conductive metal used in the conductive paste include metals such as silver, copper, nickel, aluminum, iron, gold, stainless steel, tungsten, chromium and titanium, or alloys combining two or more of these metals. Although it can be used, it is preferable to use silver, copper, nickel, or the like, and it is particularly preferable to use a silver paste, from the viewpoints of conductivity, ease of resin dispersion, cost, and the like. The conductive metal may be in the form of particles, flakes, or a mixture thereof, and flakes having a low specific resistance are particularly excellent.

As the binder resin in which the conductive metal is dispersed, for example, the thermoplastic resins exemplified as being preferably used in the resin base material and copolymers thereof can be preferably used. In addition to these, acrylic monomers, epoxy acrylates, urethane acrylates, polyether acrylates, polyester acrylates and the like can be used as the polymerizable monomer. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent in terms of adhesion to a resin substrate, and examples of the epoxy acrylate include the compounds exemplified as the epoxy acrylate copolymerized with the above acrylic resin. To be These polymerizable monomers can be used in combination with the thermoplastic resin. On the other hand, in addition to these polymerizable monomers,
It is possible to add a thermosetting resin such as phenol resin, melamine resin, epoxy resin or xylene resin. If necessary, two or more of these polymers may be copolymerized, or two or more of them may be blended and used.

These binder resins can be used by dissolving them in a general-purpose solvent, or stirring and mixing with a metal dispersant or the like without using a solvent. As a solvent,
Acetone, diethyl ketone, methyl amyl ketone, ketone-based solvent such as cyclohexanone, toluene, aromatic solvent such as xylene, methyl cellosolve, methyl cellosolve acetate, cellosolve solvent such as ethyl cellosolve acetate, ethyl lactate, butyl acetate, Isoamyl acetate,
Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ester solvents such as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methanol, ethanol, propanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, etc. Alcohol-based solvent, etc. alone or 2
A combination of more than one type can be used.

Further, the conductive paste used in the present invention may contain a dispersant, a thixotropy-imparting agent, a defoaming agent, a leveling agent, a diluent, a plasticizer, an antioxidant and a metal deactivating agent, if necessary. Additives such as agents, coupling agents and fillers may be included.

The conductive material of the present invention may be the above-mentioned conductive paste plated with metal. That is, the electromagnetic wave shielding property can be further improved by plating the surface of the conductive material filling the concave portion of the resin base material. As a method for performing metal plating, any of ordinary electrolytic plating and electroless plating is possible. The types of plated metal are gold,
Although silver, copper, nickel, aluminum, etc., or alloys thereof are possible, silver, copper, nickel or gold is preferable, and copper or nickel is most suitable for the same reason as above. The plating thickness range is 0.1-100
μm is suitable, and 0.5 to 50 μm is more preferable. If the plating thickness is less than 0.1 μm, sufficient shielding may not be exhibited due to insufficient conductivity. If the plating thickness exceeds 100 μm, the viewing angle becomes narrow, which is not preferable.

FIG. 2 is a sectional view schematically showing an example of the electromagnetic wave shielding material of the present invention. As shown in FIGS. 9A and 9B, in the electromagnetic wave shield material (10), the concave portion of the resin base material (1 or 11 and 12) has a conductive material (2).
It is filled with. Although not shown in the drawings, the electromagnetic wave shielding material (10) can be used by laminating it in multiple layers.

Next, the manufacturing method of the present invention for manufacturing the above electromagnetic shielding material of the present invention will be described. The manufacturing method of the present invention includes a step of forming a concave portion on at least one surface of the resin base material, and a step of filling the concave portion with a conductive material. Recesses (13) in the resin base material (1)
The method of forming the substrate is not particularly limited, but for example, the substrate (1
2) A convex side of a plate (made of stainless steel or the like) having a resin layer (11) applied and formed thereon to have a predetermined coating thickness and having a convex portion forming an arbitrary geometrical figure on the resin layer surface. After the resin layer is cured and the resin layer is cured, the plate having the above-mentioned convex portion is peeled and removed, whereby concave portions having a desired shape, line width, line interval, and depth corresponding to the convex portion of the plate can be preferably formed .
Also in the case of the resin base material (1) having no substrate (12), the resin layer may be peeled off from the substrate after the concave portion is similarly formed on a suitable base material. If it is a curable resin,
The resin (solution) before curing may be poured into a mold having convex portions to cure it, or a thermoplastic resin may be formed by melting a molten resin or film.

As a method for burying the conductive material in the recess formed as described above, a screen printing method, an intaglio offset printing method, a roll coater or the like can be generally used. In screen printing, the conductive paste is passed through a plate such as a mesh plate made by adding an emulsion to a mesh to form a mask pattern, or a meshless metal plate made by forming an emulsion pattern on a meshless metal plate to form a mask pattern. A pattern is typically printed.

After the conductive material is filled in the recesses as described above, if the conductive material remains in the portions other than the recesses,
Preferably, the conductive material attached to a portion other than the recess is removed. The removing method is not particularly limited, and a squeegee, a doctor blade, a cloth brush, a sponge or the like can be used. Further, when the conductive material contains a solvent, it is preferable to remove the solvent by drying it at a temperature according to the kind of the solvent by an ordinary method. Further, when the conductive material contains a curable resin, it is preferable to cure the resin by predetermined heat or radiation. Such steps can be preferably performed in the order of drying, removal and curing, or in the order of drying, curing and removal. The thickness of the conductive material filling the recess is
It is preferably 0.1 μm or more after the solvent is dried.
If it is less than 0.1 μm, the surface resistance tends to be high and the electromagnetic wave shielding effect tends to be low. Further, from the viewpoint of workability and electromagnetic wave shielding property, it is more preferable that the thickness is 1 μm or more and 500 μm or less. Note that the conductive material may be filled up to the depth of the recess, or a gap may be formed above the recess.

In the electromagnetic wave shielding material of the present invention, a transparent protective layer is formed on the surface on the side where the conductive material is embedded to protect the conductive material and to make fine scratches generated in the polishing step transparent. It may have been done. In addition, either one side (the side where the conductive material is embedded / the side where the conductive material is not embedded) or both sides is attached to the transparent supporting substrate (plastic plate or glass plate) of the electromagnetic wave shielding structure or the display surface. An adhesive layer for the above may be further laminated. These layers can be laminated and formed by a hot press, a method of passing between rolls of a roll laminator, or the like. Generally, the processing conditions at this time are a temperature of 20 to 200 ° C. and a pressure of 1 × 10. ⁴ to 4 x 1
Although it is about 0 ⁶ N / m ² , it is preferable to select suitable conditions depending on the type of resin used. Time is 0.
It may be 5 seconds or more. More preferable conditions are:
It is selected from the range of ⁶⁰ to 150 ° C. and the pressure of 1 × 10 ⁵ to 1 × 10 ⁶ N / m ² , and the time may be 10 seconds or more. The transparent protective layer is preferably a film appropriately selected from the above-mentioned plastic films for substrates, and these protective films can be attached to each other using an adhesive (described later).

As the adhesive used for laminating the above-mentioned adhesive layer and the film or the like in the present invention, for example, an acrylic polymer which is resistant to yellowing for long-term use and has good weather resistance is preferably used. The acrylic polymer is an alkyl acrylate having an alkyl group having 1 to 24 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, diethylpropyl acrylate, ethylhexyl acrylate, dodecyl acrylate, tetradecyl acrylate, and 2 -Nitro-
Nitroalkyl acrylates such as 2-methylpropyl acrylate, cycloalkyl acrylates such as cyclohexyl acrylate and trimethylcyclohexyl acrylate, hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxypropyl acrylate, alkoxyalkyl acrylates such as ethoxypropyl acrylate, glycidyl acrylate and acrylic acid. , Acrylamide, methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, diethylpropylmethacrylate, ethylhexylmethacrylate, decylmethacrylate, tetradecylmethacrylate, diethylpropylmethacrylate, etc., alkyl methacrylate having an alkyl group having 1 to 24 carbon atoms, 2 Nitroalkyl methacrylate such as nitro-2-methylpropyl methacrylate, cycloalkyl methacrylate such as cyclohexyl methacrylate, trimethylcyclohexyl methacrylate, hydroxyalkyl methacrylate such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkoxyalkyl methacrylate such as ethoxypropyl methacrylate, glycidyl methacrylate, It is a polymer obtained by using acrylic monomers such as methacrylic acid and methacrylamide alone or in combination of two or more kinds. For example, as a homopolymer, polyethyl acrylate (n = 1.4
69), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly-t-butyl acrylate (n = 1.464), poly-3-ethoxypropyl acrylate (n = 1.465), poly (Oxycarbonyltetratetramethylene) (n = 1.465), polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.47)
4), polytetradecyl methacrylate (n = 1.475), poly-n-propyl methacrylate (n = 1.484), poly-
3,3,5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate (n = 1.485),
Poly-2-nitro-2-methylpropylmethacrylate (n = 1.487), poly-1,1-diethylpropylmethacrylate (n = 1.489), polymethylmethacrylate (n =
1.489) and so on. Examples of the copolymer include a block copolymer (n = 1.48 to 1.49) or a random copolymer (n = 1.48 to 1.49) in which two or more kinds of the above-mentioned (meth) acrylic monomers are combined. As the functional group monomer of the adhesive, glycidyl methacrylate (glycidyl group), acrylic acid (carboxyl group), hydroxyethyl methacrylate and hydroxyethyl acrylate (hydroxyl group), acrylamide (amino group), etc. can be used. Materials may be used. In the above, n in parentheses indicates a refractive index.

From the viewpoint of good high temperature fluidity and adhesiveness, the storage modulus of the adhesive is 5 × 10 ⁵ P at 25 ° C.
It is preferably a or more and 5 × 10 ⁴ Pa or less at 80 ° C. The adhesive composition for keeping the storage elastic modulus in the same range includes an acrylic copolymer having a weight average molecular weight of 50,000 to 1,000,000 and a weight average molecular weight of 100 to 10,
It is preferable to blend the acrylic copolymer in the range of 000, and the ratio thereof is 90/10 to 10/90 in parts by weight. If it is out of these ranges, the storage elastic modulus greatly differs from the predetermined value, and there is a possibility that the transparency or the adhesion to the adherend may be deteriorated. The adhesive used may be a cross-linking agent, a diluent, a plasticizer, an antioxidant, a filler, if necessary.
You may mix | blend additives, such as a coloring agent, a ultraviolet absorber, and a tackifier.

Further, it is preferable that the adhesive layer is provided with a peelable protective film having a surface facing the electromagnetic wave shield material subjected to a peeling treatment. In this case, the electromagnetic wave shielding material can be adhered to the adherend such as the display surface by the adhesive exposed after peeling off the protective film. Such release films include polyethylene,
Polyolefin films such as polypropylene and ethylene-vinyl acetate, silicone release films, fluorine films, polymethylpentene films and the like are preferably used. Further, a usual plastic film may be coated with a release agent such as a silicone polymer and used.

Next, the electromagnetic wave shielding structure of the present invention will be described. FIG. 3 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding structure of the present invention. As shown in FIG. 3, the potential shielding structure (20) which is an aspect of the present invention is transparent. An electromagnetic wave shielding material (10) is laminated on one surface of a transparent support substrate (3) such as a plastic plate or a glass plate.
Although not shown in the drawing, in the electromagnetic wave shielding structure of the present invention in another aspect, the electromagnetic wave shielding material (10) may be laminated on both surfaces of the transparent supporting substrate (3). Further, the laminated surface of the electromagnetic wave shielding material on the transparent support substrate (3) may be on the resin side as shown in FIG. 4A or may be the side filled with a conductive material as shown in FIG. .

The pressurizing condition at that time is the same as that described above. Alternatively, an adhesive may be separately applied and laminated on at least one of the laminated surfaces (surfaces facing each other) of the electromagnetic wave shielding material (10) and the transparent support substrate (3) (adhesive layer is not shown). In other words, if the resin base material or the plastic plate melts and acts as an adhesive and does not impair other essential properties, it is not necessary to use an adhesive, but in other cases, bonding is performed as necessary. Agents are used. Further, a protective film that can be peeled off is attached to at least one of the laminated surfaces, so that the protective film is peeled off during lamination, after or after peeling off the protective film,
Both can be bonded together to form an electromagnetic wave shielding structure. As the adhesive and the protective film at this time, the same ones as described above can be used. The bonding method may be a press machine or a laminator and is not particularly limited.

Specific examples of the material of the plastic plate (3) include polystyrene resin, acrylic resin, polymethylmethacrylate resin, polycarbonate resin,
Polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyetherketone resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, polyethylene terephthalate resin, etc. Examples thereof include thermoplastic resins such as thermoplastic polyester resins, cellulose acetate resins, fluororesins, polysulfone resins, polyethersulfone resins, polymethylpentene resins, polyurethane resins, and diallyl phthalate resins, and thermosetting resins. Among these, polystyrene resin, acrylic resin, polymethacrylate resin, polycarbonate resin, polyvinyl chloride resin, polyethylene terephthalate resin, and polymethylpentene resin, which are excellent in transparency, are preferably used. As the glass plate (3), silicate glass (silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, borosilicate glass) phosphate glass, borate Examples thereof include glass.

The thickness of the transparent supporting substrate is 0.5 mm to 10 mm.
The thickness of mm is preferable from the viewpoint of protection, strength, and handleability when installed on a display or the like.

An infrared absorbing agent can be interposed in the electromagnetic wave shielding material or the electromagnetic wave shielding structure as described above, if necessary. Thereby, 30MHz-1GH
In addition to the electromagnetic wave shield function of 30 dB or more required for z, the function of shielding infrared rays of 900 to 1100 m generated from the display surface that adversely affects other VTR devices operated by remote control is added. To be done. As an infrared absorber, iron oxide, cerium oxide, metal oxides such as tin oxide and antimony oxide, or indium-tin oxide (hereinafter, "ITO"), tungsten hexachloride, tin chloride, cupric sulfide, chromium- Cobalt complex salt, thiol-nickel complex or aminium compound, diimonium compound (trade name of Nippon Kayaku Co., Ltd.) or anthraquinone type (SIR-114), metal complex type (SIR-128, SIR-130, SIR-1).
32, SIR-159, SIR-152, SIR-16
2), nickel dithiol infrared absorbers such as phthalocyanine type (SIR-103) (above, trade name manufactured by Mitsui Chemicals, Inc.), NKX-1199 (trade name of Japan Photosensitive Dye Laboratory Co., Ltd.), and the like. Of these infrared absorbing compounds, the most effective infrared absorbing effect is cupric sulfide, ITO, aminium compound,
It is an infrared absorber such as a diimonium compound or a metal complex type.

The infrared absorbing agent is a plastic constituting the resin substrate (1), the resin layer (11), the substrate (12), or the plastic plate (3) of the electromagnetic wave shielding structure (20).
It may be contained in advance, or the infrared composition containing the infrared absorbent (dispersing the infrared absorbent in a binder resin) is applied to one or both surfaces of the resin base material, the substrate, and the transparent support substrate. Good. Further, when a transparent protective layer or an adhesive layer is further provided as described above, an infrared absorber may be contained in these layers. In that case, it is also possible to directly add and mix an infrared absorbing agent to a fluid resin composition such as a transparent protective layer and an adhesive layer by heating or pressurizing. From the viewpoint of infrared absorption effect and transparency, the addition amount thereof is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer as the main component of the transparent protective layer or the adhesive layer. Specifically, for example, the infrared absorbent layer has one or both sides of the electromagnetic wave shield material (the side on which the conductive material is not embedded) or both sides, or one side of the electromagnetic wave shield structure (the side of the electromagnetic wave shield material / the transparent support). It is formed on the substrate side) or on both sides. That is, in the case of an electromagnetic wave shielding structure composed of one electromagnetic wave shielding material and one plastic plate, the infrared absorbent layer has a surface A of the electromagnetic wave shielding material, B between the electromagnetic wave shielding material and the plastic plate, and a plastic plate. It may be formed on any surface of the surface C, or may be formed on a plurality of surfaces. Further, a new layer such as the above transparent protective layer may be optionally formed on the infrared absorbent layer, or conversely, an infrared absorbent layer may be formed on the adhesive layer or the transparent protective layer. May be. In addition, it is preferable that the infrared absorbent layer has adhesiveness because workability and workability are easy.

As the binder resin in which the infrared absorber is dispersed, for example, epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac type epoxy resin, polyisoprene, poly-
Diene resins such as 1,2-butadiene, polyisobutene and polybutene, polyacrylate copolymers composed of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, polymethyl methacrylate, etc., polyvinyl acetate, polyvinyl propylene Polyester resins such as pionate, polyolefin resins such as polyethylene, polypropylene, polystyrene and ethylene-vinyl acetate copolymer are used. The blending amount at that time is 0.01 to 10 parts by weight of the infrared absorber with respect to 100 parts by weight of the binder resin.
It is preferably part by weight, more preferably 0.05 to 5 parts by weight. If the blending amount is less than 0.01 part by weight, the infrared ray shielding effect is small, and if it exceeds 10 parts by weight, there is a possibility that poor dissolution or deterioration of transparency may occur.

The infrared composition is applied so that the infrared absorbent layer preferably has a thickness of 0.1 to 30 μm.
The applied infrared composition can be cured by using heat, ultraviolet rays or the like depending on the kind of the binder resin.

If necessary, the electromagnetic wave shielding material or the electromagnetic wave shielding structure of the present invention further comprises an antireflection layer for preventing visible light reflection and increasing visible light transmittance, and flickering of a display. As the anti-glare layer for preventing feeling and tiredness of eyes, any layer of the surface protective layer Tang having high abrasion resistance and high surface hardness, using known materials, as exemplified in the infrared absorbent layer. In any way
It can be formed on any surface.

Next, the electromagnetic wave shield display of the present invention will be described. The electromagnetic wave shield display of the present invention has the electromagnetic wave shield material or the electromagnetic wave shield structure of the present invention attached to the surface of the display (the front glass substrate of the display device) so that the electromagnetic waves from the display surface can be effectively shielded. Is. The attachment method is not particularly limited, and may be directly laminated / pasted on the display surface using an adhesive or the like, or may be installed on the front surface of the screen on the display via an attachment jig.

FIG. 4 is a sectional view schematically showing an example of the electromagnetic wave shield display of the present invention. The figure shows a mode in which an electromagnetic wave shielding material or an electromagnetic wave shielding structure is laminated and attached to the display surface using an adhesive. In the electromagnetic wave shield display (30),
As shown in FIG. 3A, the electromagnetic wave shielding material (10)
The display surface (4) directly through the adhesive layer (5)
It may be laminated on the sheet, or as shown in FIG.
The electromagnetic wave shielding structure (20) may be laminated to the display surface (4) via the adhesive layer (5). Also,
The stacking direction may be different from that shown in the figure. For example, the side of the electromagnetic wave shielding material (10) on which the conductive material is not embedded, or the electromagnetic wave shielding structure (20).
The transparent support substrate (3) side may be attached to face the display surface (4). The electromagnetic wave shield display is used in a state where the conductive material of the electromagnetic wave shield material and the external electrode are connected by any method for grounding. From the viewpoint of easy grounding, as shown in FIG. 4, it is preferable that the electromagnetic wave shielding material or the electromagnetic wave shielding structure has the conductive material side attached to the display surface side.

The electromagnetic wave shield material according to the present invention is characterized by comprising a resin base material having a recess and a conductive material filling the recess. For example, according to the conventional printing method, line accuracy is deteriorated due to ink bleeding when a circuit is drawn with conductive ink, whereas in the present invention, recesses having a desired line width and line spacing are formed in advance. Since the conductive material is filled in the concave portion of the resin base material, the conductive material portion having a highly accurate line width and line interval is formed, and therefore, the electromagnetic wave shielding material excellent in transparency and non-visibility. Can be realized. In the present invention, being transparent means that when an object is viewed through it, the shape and color of the object do not change as compared to when they do not pass through it. The recess may be provided on at least one surface of the resin base material. Since the concave portion having an arbitrary shape can be freely formed on the resin base material, the conductive member can be appropriately arranged in a form necessary for making the electromagnetic wave shielding property sufficient. Furthermore, since the thickness and characteristics of the resin base material having the concave portions can be arbitrarily set so as to easily follow the irregularities of the adherend, it is possible to prevent electromagnetic wave leakage from the gap with the adherend.

[0064]

EXAMPLES Next, the embodiments of the present invention will be described more specifically based on examples, but the present invention is not limited to these. Hereinafter, “part by weight” is simply referred to as “part”. (Example 1) <Manufacture of plate 1> Copper foil (trade name: SQ-VLP 35 µm, manufactured by Mitsui Kinzoku Co., Ltd.) was mirror-polished. The surface roughness of the polished surface is JIS K 7104 (measurement distance 8 mm).
R _Z is 0.10 μm, R _max is 0.15 μm, and R _a is 0.
It was 05 μm. Electroless nickel plating having the following composition and pH was applied to the polished copper foil at a liquid temperature of 90 ° C. for 12 minutes. The plating thickness was 5 μm. (Composition of electroless nickel plating solution) Nickel sulphate ……………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………… ………………………… 5 Then, electrolytic copper plating with the following composition was applied on the nickel plating. The liquid temperature was room temperature and the cathode current density was 4 A / dm ² and the anode current density was 24 A / dm ² for 25 minutes. The plating thickness was 15 μm. (Electrolytic copper plating composition) Copper sulphate ………………………… 220g / l Sulfuric acid ……………………………… 60g / l DRY FILM (trade name HN-225, Nichigo) Manufactured by K.K.) at a temperature of 100 ° C and a linear pressure of 0.5 kg / c.
and the line speed was 0.5 m / min. Furthermore, 200 × 200mm, line width 30μ
m with a negative film of 250 μm in pitch, 70 m
Exposure was performed under the condition of J / cm ² . After developing, copper is etched at a liquid temperature of 50 ° C. using an alkaline etchant having the following composition to obtain a line width of 20 μm and a line pitch of 2 μm.
A plate having a size of 50 μm and a line height of 15 μm was obtained. (Alkaline etchant composition) Copper chloride ………………………… 175g / l Ammonium hydroxide …… 154g / l Ammonium chloride …… 236g / l

<Production Example of Electromagnetic Wave Shielding Material 1 and Electromagnetic Wave Shielding Structure 1> Polyethylene terephthalate (PET) film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd.,
On one side of the product name A-4100), the following resin composition 1
PE having a resin layer, which was applied at room temperature using an applicator to a predetermined dry application thickness (thickness 20 μm).
A T film was created. On the resin layer thus obtained, the plate (200 × 200 mm, line width 20
The sides of the geometric figures having a size of μm, a pitch of 250 μm, and a line height of 15 μm) were superposed and laminated at a pressure of 0.5 Mpa. After this, 0.5 J / cm ² UV from the top of the film
Was irradiated to cure the resin, and the above plate was peeled and removed to obtain a PET film having a resin layer on which irregularities were formed. PE having a resin layer on which the obtained uneven shape is formed
The surface roughness of the convex surface of T is JIS K 7104 (measuring distance 8 mm), R _Z is 0.10 μm, and R _max is 0.15.
μm and _Ra were 0.05 μm. Screen printing method [screen printing machine (made by New Long Precision Co., Ltd., LS-34GX with alignment device), nickel alloy meshless metal plate (made by Mesh Industry Co., Ltd., thickness Fifty
μm, pattern size 8 mm × 8 mm) and permalex metal squeegee (imported from Tomoe Kogyo Co., Ltd.)] were used to bury the conductive silver paste TC-2100 (trade name of Hitachi Chemical Co., Ltd.). After drying the solvent, 1
It was heated and cured at 50 ° C. for 30 minutes to obtain an electromagnetic wave shield film 1. In addition, the conductive material attached to other than the recess was removed using a cloth brush. On the side of the electromagnetic wave shielding film 1 where the conductive material was buried, a commercially available acrylic plate (COMO glass; Co., Ltd.) via a polyvinyl butyral (PVB) sheet # 5000A (trade name of Denki Kagaku Kogyo Co., Ltd., thickness 0.4 mm) was used. Kuraray product name, thickness 3m
m, n = 1.49) at 110 ° C., 20 Kgf / cm ² ,
An electromagnetic wave shielding structure 1 was obtained by thermocompression bonding under the condition of 15 minutes and pasting.

<Resin Composition 1> To a 500 cm ³ three-necked flask equipped with a thermometer, a cooling tube and a nitrogen introducing tube, 200 cm ^{3 of} toluene, 20 g of methyl methacrylate (MMA),
Butyl acrylate (BA) 35g, acrylamide (A
M) 2 g, bidroxyethyl methacrylate (HEM
A) 5 g and AIBN 250 mg were added, and the mixture was stirred under reflux at 100 ° C. for 3 hours while bubbling with nitrogen.
Next, 5 g of 2-methacryloyloxyethyl isocyate (trade name Karenz MOI, Showa Denko KK) and 0.1 g of tin desolvent were added and reacted at 80 ° C. for 2 hours. Then, it was reprecipitated with methanol, and the polymer as a reaction product was filtered and then dried under reduced pressure to obtain a UV-curable polyacrylic ester. Obtained polyacrylic acid ester (MMA / BA / AM / HEMA = 32/57/3 /
(8, Mw = 30,000) 100 parts by weight as a photopolymerization initiator
-Methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one (trade name Irgacure 90
7, 1 part of Ciba Geigy Co., Ltd., and 150 parts of toluene were added to prepare a resin composition 1.

(Example 2) <Electromagnetic wave shielding film 2 and electromagnetic wave shielding structure 2
Preparation Example> The resin composition 1 was applied to one side of a PET film having a thickness of 50 μm at room temperature using an applicator,
It was dried by heating at 90 ° C. for 20 minutes. On the obtained resin layer (thickness 35 μm), a stainless plate (200 × 200 m)
m, line width 10 μm, pitch 50 μm, line height 1
0 μm) were superposed and laminated at a pressure of 0.5 Mpa. Then, the resin composition is applied to the film from above 1.0.
After being irradiated with UV of J / cm ² to be cured, the stainless plate was peeled and removed. In the same manner as in Example 1, the PET film was filled with the same conductive paste as in Example 1 by the screen printing method. Using heat press machine
A PVB sheet was prepared by mixing 0.1% by weight of a near-infrared absorber (trade name: NKX-1199, manufactured by Japan Photosensitive Dye Research Institute), and the obtained electromagnetic wave shielding film had the conductive material side of the PVB sheet. Laminate so that it contacts the surface, and use a heat press machine at 120 ° C, 30 Kgf / cm
^{The two} were heat-pressed under conditions of ² and 30 minutes to obtain an electromagnetic wave shielding film 2. The PVB sheet surface of the electromagnetic wave shielding film 2 thus produced is a commercially available acrylic plate (COMO glass; product name by Kuraray Co., Ltd., thickness 3 mm)
Are laminated so that they contact each other at 120 ° C., 30 Kgf /
An electromagnetic wave shielding structure 2 was obtained by thermocompression bonding using a heat press machine under conditions of cm ² and 30 minutes.

(Example 3) The electromagnetic wave shielding film 3 and the electromagnetic wave shielding structure 3 were prepared in the same manner as in Example 1 except that the following resin composition 3 was used instead of the resin composition 1 of Example 1. Was produced. <Resin composition 3> The composition of the polyacrylic ester is M
MA / BA / AM / hydroxyethyl acrylate = 20
The monomer was polymerized under the same conditions as in the resin composition 1 so as to be / 65/7/3/5 to obtain a UV-curable polyacrylic acid ester with Mw = 7000. Using this polyacrylic ester, a resin composition 3 was prepared in the same manner as the resin composition 1.

Example 4 An electromagnetic wave shielding film 4 and an electromagnetic wave shielding structure 4 were prepared in the same manner as in Example 1 except that the following resin composition 4 was used instead of the resin composition 1 of Example 1. Was produced. <Resin composition 4> 35 parts of neopentyl glycol diacrylate, trimethylolpropane triacrylate 4
0 part, urethane acrylate (obtained by reacting 1 mol of polytetramethylene glycol with 2 mol of tolylene diisocyanate and then reacting with 2 mol of hydroxyethyl methacrylate) 22 parts, 1-hydroxy-cyclohexyl as a photoinitiator -Phenyl-ketone (trade name Irgacure 184, Ciba-Geigy Co., Ltd.) 3 parts was blended to obtain a resin composition 4.

(Example 5) Instead of the resin composition 1 of Example 1, a polybutadiene elastomer (Polybd R) was used.
-45HT: an electromagnetic wave shielding film 5 and an electromagnetic wave shielding structure 5 were produced in the same manner as in Example 1 except that -45HT: trade name of Idemitsu Petrochemical Co., Ltd.) was used.

(Example 6) Byron-200 (trade name, manufactured by Toyobo Co., Ltd., Mn = 15, 0) was used in place of the polyacrylic acid ester as the main component of the resin composition 1 of Example 1.
00, linear saturated polyester resin) was used, and the resin composition 6 was prepared in the same manner except for the above. The above resin composition 6
Was applied on a PET film in the same manner as in Example 1, the geometrical surface side of the same stainless steel plate as in Example 1 was superposed on the resin layer, and hot-pressed under the conditions of 110 ° C., 20 Kgf / cm ² , and 15 minutes. It thermocompression-bonded using the machine. Then, the plate having the convex geometrical figure was peeled off. After that, the electromagnetic wave shielding film 6 and the electromagnetic wave shielding structure 6 were produced in the same manner as in Example 1.

(Embodiment 7) PE is used as a plastic film.
T (50 μm) to polycarbonate film (50 μm
m,), the electromagnetic wave shielding film 7 and the electromagnetic wave shielding structure 7 were obtained in the same manner as in Example 1 except that the thickness of the resin layer was changed from 35 μm to 15 μm.

(Embodiment 8) Using a stainless steel plate having convex shapes of different line sizes, the line width of geometric figures was changed from 20 μm to 30 μm, the line interval was changed from 250 μm to 500 μm, and the thickness of resin layer was changed from 20 μm to 20 μm. 15 μm
An electromagnetic wave shielding film 8 and an electromagnetic wave shielding structure 8 were obtained in the same manner as in Example 3 except that the above was changed.

(Embodiment 9) As a conductive paste, a paste whose conductive metal is copper (trade name: CPC-8000,
Other than using Sumitomo Bakelite Co., Ltd.,
In the same manner as in Example 1, an electromagnetic wave shielding film 9 and an electromagnetic wave shielding structure 9 were obtained.

Comparative Example 1 The same PET film as in Example 1 was used, except that neither resin layer nor recesses were formed on the same PET film. Then, using the same conductive paste as in Example 1, the line width is 20 μm and the pitch is 250 μm.
An electromagnetic wave shielding film and an electromagnetic wave shielding structure were obtained in the same manner as in Example 1 except that the conductive material layer was directly formed on the PET film by the screen printing method using the screen mesh of 1.

With respect to the electromagnetic wave shielding films of Examples and Comparative Examples obtained as described above, the electromagnetic wave shielding property, visible light transmittance, non-visibility, infrared shielding property, and before and after the heat treatment of the electromagnetic wave shielding structure were obtained. The adhesive properties were measured as follows. The electromagnetic wave shielding property is a coaxial waveguide converter (manufactured by Japan High Frequency Co., Ltd., TWC-S-024).
The sample was inserted between the flanges and the spectrum analyzer (manufactured by YHP, 8510B vector network analyzer) was used to measure at a frequency of 30 MHz to 1 GHz. The visible light transmittance was 400 to 400 using a double beam spectrophotometer (manufactured by Hitachi, Ltd., model 200-10).
The average value of the transmittance of 700 nm was used. The non-visibility is evaluated by observing the electromagnetic wave shielding structure with the naked eye from a place 0.5 m away and recognizing the geometric figure formed of the conductive material. Was NG. The infrared shielding rate is 900-using a spectrophotometer (U-3410 manufactured by Hitachi, Ltd.).
The average value of infrared absorptance in the region of 1,100 nm was used.

The adhesive strength was measured using a tensile tester (Tensilon UTM-4-100, manufactured by Toyo Baldwin Co., Ltd.) with a width of 10 mm, a 90 ° direction and a peeling speed of 50 mm / min.

The results are shown in Table 1.

[Table 1] In Comparative Example 1, since the conductive paste was directly printed on the PET film by the screen printing method, the line width was significantly thicker than the desired value, resulting in visible light transmittance and non-visibility. Was inferior to On the other hand, all of the electromagnetic wave shielding films in which the conductive paste was embedded on the resin base material having the concave portions showed favorable characteristics.

[0079]

According to the method of manufacturing an electromagnetic wave shielding material of the present invention, a conductive material portion having a desired line width and line spacing is formed on a resin base material so as not to be visually recognized by the naked eye and the transparency is not impaired. It can be formed with high precision. Therefore, in the electromagnetic wave shielding material of the present invention in which the conductive material portion having such a desired line width and line spacing is accurately formed on the resin substrate, the optical characteristics such as visible light transmittance and non-visibility are It is good. Since the electromagnetic wave shielding material and the electromagnetic wave shielding structure of the present invention are excellent in electromagnetic wave shielding property, transparency and non-visibility, the display of the present invention to which these are attached is almost in the normal state without increasing the brightness. Under similar conditions, clear images can be comfortably viewed. Also, in addition to the display surface, measuring devices that generate electromagnetic waves or need to be protected from electromagnetic waves, such as windows and casings that look into the inside of measuring instruments and manufacturing equipment, especially windows that require transparency, The electromagnetic wave shielding material or the electromagnetic wave shielding structure of the present invention can be provided and used effectively in any place where it is necessary to block electromagnetic waves.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of a resin base material used for an electromagnetic wave shield material of the present invention.

FIG. 2 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding material of the present invention.

FIG. 3 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding structure of the present invention.

FIG. 4 is a sectional view schematically showing an example of the electromagnetic wave shield display of the present invention.

[Explanation of symbols]

1 resin base material 2 Conductive material 3 Transparent support substrate 4 display 10 Electromagnetic wave shield material 20 Electromagnetic wave blocking structure 30 Electromagnetic wave shield display Conductive material embedded in a geometric pattern

Continued front page    F-term (reference) 4F100 AB16B AB16C AB16E AB17A                       AB17E AB24E AB33B AB33C                       AK41 AS00A AT00E BA03                       BA04 BA05 BA07 BA10A                       BA10C BA10E EC03 EC032                       EC04 EC042 EH46 EH462                       EJ15C EJ42 EJ422 EJ54                       EJ542 EJ86 EJ862 GB41                       HB00E JB13E JB14E JD02B                       JD08 JG01E JG04E JK14A                       JM01E JN01 JN02 YY00E                 5E321 AA04 BB23 CC16 GG05 GH01                 5G435 AA01 AA17 GG33 HH02 HH12                       KK07

Claims (26)

[Claims] 1. A method of manufacturing a plate for forming unevenness, which comprises drawing a geometrical figure by etching an etching layer of a laminate in which a carrier layer, a barrier layer and an etching layer are sequentially laminated. 2. A laminate in which a carrier layer, a barrier layer, and an etching layer are sequentially laminated is a carrier layer of JIS.
K R _Z of 7104 forms a barrier layer on the surface of a is the surface roughness 0.01 to 0.1 m, further versions on etch layer formed claim 1 which has been manufactured according to the Production method. 3. The barrier layer is a layer that is not substantially etched by etching the etching layer.
Or the method for producing the plate according to 2. 4. The material of the etching layer is copper, and the material of the barrier layer is nickel or nickel alloy.
4. The method for producing the plate according to any one of 3 to 3. 5. The etching is performed by a photolithographic method using an alkaline etchant.
Method for producing the described plate. 6. The carrier layer is made of copper foil.
A method for producing a plate according to any one of 1. 7. The method for producing a plate according to claim 1, wherein the carrier layer is made of copper foil whose surface in contact with the barrier layer is polished. 8. A plate for forming irregularities produced by the method according to claim 1. 9. A plate for forming unevenness, which comprises a layer for drawing a geometrical figure formed on a barrier layer. 10. The plate according to claim 9, further comprising a carrier layer below the barrier layer. 11. The surface of the carrier layer in contact with the barrier layer has an R _Z of 0.01 to 0.1 μ of JIS K 7104.
A plate according to claim 10, having a surface roughness of m. 12. The plate according to claim 9, wherein the material of the layer forming the geometric figure is an etchable layer, and the barrier layer is a layer which is not substantially etched by this etching. 13. The plate according to claim 12, wherein the material forming the geometrical figure is copper, and the material forming the barrier layer is nickel or a nickel alloy. 14. The plate according to claim 9, wherein the geometric pattern has a line width of 0.1 μm or more and 50 μm or less and a line interval of 10 μm or more. 15. The plate according to claim 14, wherein the depth of the recess is 0.1 μm or more. 16. A step of transferring the geometrical figure of the plate according to claim 8 to at least one surface of a resin base material, and filling a conductive material in a concave portion formed in the resin base material. A method of manufacturing an electromagnetic wave shield material, comprising: 17. The conductive material has a specific resistance value of 1.0 × 1.
The method for producing an electromagnetic wave shield material according to claim 16, which has a resistivity of 0 ⁻⁴ Ω · cm or less. 18. The method for producing an electromagnetic wave shield material according to claim 16, wherein the conductive material is a conductive paste, or the conductive paste is plated with a metal. 19. The method for producing an electromagnetic wave shield material according to claim 16, wherein the conductive paste is a silver paste, a copper paste, a nickel paste or a gold paste. 20. The method for producing an electromagnetic wave shield material according to claim 18, wherein the conductive paste is a paste that is cured by heat or radiation. 21. The conductive material embedded in the recess of the resin substrate is electrically connected as a whole.
0. The method for producing an electromagnetic wave shield material according to any one of 0. 22. A resin base material is a resin that is cured by radiation,
At least one of thermosetting resin or thermoplastic resin
The method for producing an electromagnetic wave shield material according to any one of claims 16 to 21, which comprises a seed. 23. An electromagnetic wave shield material produced by the method according to claim 16. 24. An electromagnetic wave shielding structure comprising a transparent supporting substrate and the electromagnetic wave shielding material according to claim 23 laminated on at least one surface thereof. 25. An electromagnetic wave shield display, wherein the electromagnetic wave shield material according to claim 23 is attached to a display surface. 26. An electromagnetic wave shield display, wherein the electromagnetic wave shield structure according to claim 24 is attached to a display.