JP2000323889A - Manufacture of electromagnetic wave shielding adhesive film, electromagnetic wave shielding component, and electromagnetic wave shielded display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for an electromagnetic wave shielding adhesive film of good electromagnetic wave shielding characteristics, transparency/non-visibility, and adhesion. SOLUTION: In manufacturing an electromagnetic wave shielding adhesive film, related to a plastic film with a conductive metal where a conductive metal layer is laminated on a transparent base material through a thermo-setting adhesive layer, an etching resist pattern is formed by screen printing or offset printing, and the conductive metal layer is etched to form a geometric graphic of a conductive metal.

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 adhesive film having a shielding property for electromagnetic waves generated from the front surface of a display such as a CRT, a PDP (plasma), a liquid crystal, an EL, etc., an electromagnetic wave shielding structure and an electromagnetic wave shielding display. About the law.

[0002]

2. Description of the Related Art In recent years, with the increase in the use of various types of electrical equipment and electronic equipment, electromagnetic noise interference has been increasing steadily. Noise can be broadly divided into conducted noise and radiated noise.
There is a method using a noise filter or the like. On the other hand, as a countermeasure against radiation noise, it is necessary to electromagnetically insulate the space, so make the housing a metal body or a highly conductive body, insert a metal plate between circuit boards, Is wrapped with metal foil. With these methods, an electromagnetic wave shielding effect of a circuit or a power supply block can be expected, but it cannot be applied to an electromagnetic wave shielding generated from the front of a display such as a CRT or PDP because it is opaque.

As a method for achieving both the electromagnetic wave shielding property and the transparency, a method of forming a thin film conductive layer by depositing a metal or metal oxide on a transparent substrate (Japanese Patent Laid-Open No. 27880/1990).
No. 0, JP-A-5-323101). On the other hand, an electromagnetic wave shielding material in which a good conductive fiber is embedded in a transparent substrate (JP-A-5-327274,
JP-A-5-269912) or an electromagnetic wave shielding material in which a conductive resin containing metal powder or the like is directly printed on a transparent substrate (JP-A-62-57297, JP-A-2-5-5).
Further, an electromagnetic wave shielding material in which a transparent resin layer is formed on a transparent substrate such as polycarbonate having a thickness of about 2 mm and a copper mesh pattern is formed thereon by an electroless plating method (see Japanese Patent Application Laid-Open No. 5-2838
No. 89) has been proposed.

[0004]

As a method for achieving both the electromagnetic wave shielding property and the transparency, Japanese Patent Application Laid-Open No. 1-278800 has been disclosed.
In the method of forming a thin film conductive layer by depositing a metal or metal oxide on a transparent substrate disclosed in Japanese Patent Application Laid-Open No. 100 ° to 2,000 °), the surface resistance of the conductive layer becomes too large, so that the shielding effect of 30 dB or more required at 30 MHz to 1 GHz exceeds 20 dB.
The following were insufficient. In an electromagnetic wave shielding material in which a good conductive fiber is embedded in a transparent base material (JP-A-5-327274 and JP-A-5-269912), 30 MHz is used.
Although the shielding effect of the electromagnetic wave of 1 GHz to 1 GHz is sufficiently large as 40 to 50 dB, the fiber diameter required for regularly arranging the conductive fibers so as to prevent the leakage of the electromagnetic wave is too large at 35 μm. It was not suitable for display applications. In addition, Japanese Unexamined Patent Publication
Similarly, in the case of an electromagnetic wave shielding material in which a conductive resin containing a metal powder or the like disclosed in JP-A-2-57297 and JP-A-2-52499 is directly printed on a transparent substrate, the line width is about 100 μm due to the limit of printing accuracy. This was not suitable because visibility was developed. Further, JP-A-5-28
No. 3889 discloses a shield material in which a transparent resin layer is formed on a transparent substrate such as polycarbonate having a thickness of about 2 mm and a copper mesh pattern is formed thereon by an electroless plating method. In order to secure the force, it is necessary to roughen the surface of the transparent substrate. Generally, a highly toxic oxidizing agent such as chromic acid or permanganic acid must be used as the roughening means.
With resins other than BS, it is difficult to achieve satisfactory roughening. Even if electromagnetic wave shielding properties and 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 method for forming a film. Furthermore, if the transparent substrate is thick, it cannot be brought into close contact with the display, so that leakage of electromagnetic waves therefrom increases. In addition, in terms of manufacturing, there is also a drawback that the shield material cannot be made into a scroll or the like, so that it becomes bulky, and is not suitable for automation, so that the manufacturing cost increases. Regarding the shielding properties of electromagnetic waves generated from the front of the display, in addition to the electromagnetic wave shielding function of 30 dB or more at 30 MHz to 1 GHz, the infrared rays of 900 to 1,100 nm generated from the front of the display can be transmitted to other VTR devices operated by remote control. It has to be shielded because it has an adverse effect. In addition to this, not only good visible light transmittance and high visible light transmittance, but also the adhesiveness that can be stuck to the display surface to prevent leakage of electromagnetic waves, and the presence of shielding material should be visually checked. Invisibility, a characteristic that cannot be achieved, is also required. As for the adhesiveness, it is necessary to easily adhere to glass or a general-purpose polymer plate at a relatively low temperature and have good adhesiveness over a long period of time. However, no satisfactory adhesive film has been obtained so far that simultaneously satisfies the characteristics such as electromagnetic wave shielding property, infrared ray shielding property, transparency / invisibility, and adhesiveness. In view of the above, an object of the present invention is to provide a method for manufacturing an electromagnetic wave shielding adhesive film, an electromagnetic wave shielding structure, and an electromagnetic wave shielding display having electromagnetic wave shielding properties, transparency and invisibility, and good adhesive properties. I do.

[0005]

The present invention relates to the following. (1) An etching resist pattern formed by a screen printing method or an offset printing method is formed on a plastic film with a conductive metal formed by laminating a conductive metal layer on a transparent substrate via a thermosetting adhesive layer. And forming a geometric figure made of a conductive metal by etching the conductive metal layer. (2) The method for producing an electromagnetic wave shielding adhesive film according to (1), wherein the degree of curing of the thermosetting adhesive layer is less than 60%. (3) The method for producing an electromagnetic wave shielding adhesive film according to (1) or (2), wherein the thermosetting adhesive layer has a refractive index of 60% or more and a range of 1.40 to 1.70. (4) The method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (3), wherein the thickness of the thermosetting adhesive layer is not less than the thickness of the conductive metal. (5) The method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (4), wherein the thermosetting adhesive layer contains an infrared absorbing agent. (6) The electromagnetic wave shielding property according to any one of (1) to (5), wherein the line width of the geometrical figure drawn by the conductive metal is 40 μm or less, the line interval is 100 μm or more, and the line thickness is 40 μm or less. Manufacturing method of adhesive film. (7) The method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (6), wherein the metal of the plastic film with a conductive metal is copper, aluminum or nickel having a thickness of 0.5 to 40 μm. (8) The plastic film of the plastic film with a conductive metal is a polyethylene terephthalate film or a polycarbonate film (1) to (7).
The method for producing an electromagnetic wave shielding adhesive film according to any one of the above. (9) The method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (8), wherein the conductive metal is copper, and at least the surface thereof is blackened. (10) The conductive metal is a paramagnetic metal (1) to
(9) The method for producing the electromagnetic wave shielding adhesive film according to any of (9). (11) A peelable protective film is laminated on the side opposite to the transparent substrate simultaneously with or after the application of pressure (1) to (1).
0) The method for producing an electromagnetic wave shielding adhesive film according to any one of the above items. (12) An electromagnetic wave characterized in that after the method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (11) is carried out, the obtained electromagnetic wave shielding adhesive film is bonded to a plastic plate. Manufacturing method of the shielding structure. (13) After the method for producing an electromagnetic wave shielding adhesive film described in (12) is performed, while the protective film of the obtained electromagnetic wave shielding adhesive film is being peeled off or peeled off, a plastic plate is laminated. A method for producing an electromagnetic wave shielding component, which is characterized by the following. (14) After performing the method for producing an electromagnetic wave shielding adhesive film according to any one of (1) to (11), the obtained electromagnetic wave shielding adhesive film is bonded to a display surface. Manufacturing method of shielded display. (15) After performing the method for producing an electromagnetic wave shielding adhesive film according to (12), the protective film of the obtained electromagnetic wave shielding adhesive film is peeled or peeled, and then bonded to a display surface. Characteristic manufacturing method of electromagnetic wave shielding display.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent substrate used in the present invention may be a plastic plate, a glass plate or the like, but is preferably a flexible one, for example, a plastic film. Examples of the plastic film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene, polypropylene, polystyrene and EVA; vinyl resins such as polyvinyl chloride and polyvinylidene chloride; polysulfone and polyether sulfone. And plastics such as polycarbonate, polyamide, polyimide, and acrylic resin. The transparent substrate preferably has a total visible light transmittance of 70% or more and a thickness of 1 mm or less. The transparent substrate may be used in a single layer, but may be used as a multilayer body by combining two or more layers. Among the plastic films, a polyethylene terephthalate film or a polycarbonate film is preferable in terms of transparency, heat resistance, ease of handling, and price. As for the thickness of a transparent base material, especially as for the thickness of a plastic film, 5-500 micrometers is preferable. If it is less than 5 μm, the handleability tends to deteriorate, and if it exceeds 500 μm, the transmittance of visible light tends to decrease. The thickness of the transparent substrate, especially the thickness of the plastic film, is 1
More preferably, it is 0 to 200 μm.

[0007] The thermosetting adhesive layer used in the present invention is formed by a crosslinking reaction or a curing reaction between a resin and a cross-linking agent or a curing agent by heat, and by a self-curing of the resin by heat.
An adhesive composition having a three-dimensional network structure. Geometric figures drawn with conductive metal, an electromagnetic wave shielding adhesive film having a thermosetting adhesive layer and a transparent base material as a basic configuration, it is preferable to adhere this to a display or a plastic plate as an adherend. For that, the adhesive layer must flow. It is desirable that the adhesive layer be fluidized at room temperature or heated to adhere to the adherend. It is desirable that the adhesive layer be subjected to a crosslinking reaction or a curing reaction by heat after or simultaneously with the bonding. For this reason, the thermosetting adhesive layer needs to flow when it is adhered to a display or a plastic plate as an adherend, and the degree of curing is preferably less than 60%. Even a crosslinked or cured adhesive composition can be used as long as it can flow by heating and pressurizing and has adhesiveness.
Any material having a viscosity of 10,000 poise or less at 200 ° C. by a rotational viscometer can be used.
The thermosetting adhesive layer used in the present invention is a varnish obtained by dissolving or dispersing the adhesive composition in a solvent, and coating the varnish on a support such as a plastic film or a metal foil.
Obtained by drying. In this drying step, heat is applied to the adhesive composition, and crosslinking and curing to a certain extent proceeds. If the crosslinking / curing proceeds too much, the fluidity of the adhesive layer becomes poor. Therefore, it is necessary to control the adhesive layer under appropriate conditions to obtain a fluid state.
It is preferable that the degree of cure be less than 60%. The curing degree can be measured using DSC (differential scanning calorimetry).

[0008] The DSC (differential scanning calorimetry) is based on a zero-position method of supplying or removing a calorific value so as to constantly cancel a temperature difference between a standard sample having no heat generation and heat absorption within a measurement temperature range. , And a measuring device is commercially available and can be used for measurement. The reaction of thermosetting adhesive is
This is an exothermic reaction. When the temperature of the sample is raised at a constant rate, the sample reacts and generates heat. The calorific value is output to a chart, and a heating curve and an area surrounded by the base line are obtained based on the base line, and this is defined as a calorific value.
The heating value is measured from room temperature to 200 ° C. at a heating rate of 5 to 10 ° C./min, and the above calorific value is determined. Some of these are performed automatically, and can be easily performed by using them. Next, the calorific value of the adhesive obtained by applying the adhesive varnish to the support and drying is determined as follows. First, the total calorific value of the uncrosslinked and uncured sample obtained by drying the solvent using a vacuum dryer at 25 ° C. was measured, and this was determined as A (J /
g). Next, the calorific value of the coated and dried sample was measured, and this was designated as B. Curing degree C (%) of sample (heating,
The state in which heat generation is completed by drying) is given by the following equation (1).

[0009]

## EQU1 ## C (%) = (A−B) × 100 / A

When the degree of cure is less than 60%, the network structure is not sufficiently generated, so that the adhesive layer has fluidity and can flow and adhere to the adherend. On the other hand, when the degree of cure is 6
If it is 0% or more, the fluidity of the adhesive layer is poor and the adhesiveness is poor.

As a thermosetting adhesive, for example, natural rubber,
Resins such as isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, butyl halide, acrylonitrile-butadiene rubber, styrene-butadiene rubber, polyisobutene, carboxy rubber, neoprene, and polybutadiene, and sulfur as a crosslinking agent, aniline formaldehyde resin, urea formaldehyde resin , Phenol formaldehyde resin, ligulin resin, xylene formaldehyde resin, xylene formaldehyde resin, melamine formaldehyde resin, epoxy resin, urea resin, aniline resin, melamine resin, phenol resin, formalin resin, metal oxide, metal chloride, oxime, alkylphenol resin And so on. For the purpose of increasing the speed of the crosslinking reaction, additives such as general-purpose vulcanization accelerators can be used.

The curing reaction system includes a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an unsaturated hydrocarbon group and the like, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a thiol group and the like. Is used in combination with a curing agent having a functional group of, or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide, or peroxide. For the purpose of increasing the curing reaction speed, additives such as general-purpose catalysts can be used. Specifically, acrylic resin (n = 1.45 to 1.47), unsaturated polyester resin (n = 1.52 to 1.54), saturated polyester resin (n = 1.52 to
1.54), diallyl phthalate resin (n = 1.57), epoxy resin (n = 1.55 to 1.60), furan resin (n = 1.55), polyurethane resin (n = 1.5 to 1.6) and the like.

A general-purpose thermoplastic resin may be blended in addition to the above materials. As general-purpose thermoplastic resin,
For example, natural rubber (refractive index n = 1.52), polyisoprene (n =
1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly-
2-heptyl-1,3-butadiene (n = 1.50), poly-2
-T-butyl-1,3-butadiene (n = 1.506), poly-
(Di) enes such as 1,3-butadiene (n = 1.515), polyoxyethylene (n = 1.456), polyoxypropylene (n =
1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.449), polyethers such as polyvinyl butyl ether (n = 1.456), polyvinyl acetate (n = 1.467), polyvinyl propionate (n = 1.46).
7) Polyesters such as polyurethane, polyurethane (n = 1.5-1.6),
Ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 ~
1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 to 1.6), polyethyl acrylate (n = 1.469), 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),
Polyoxycarbonyltetramethylene (n = 1.465), polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.465)
475), poly-n-propyl methacrylate (n = 1.484),
Poly-3,3,5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate (n = 1.48)
5), poly-2-nitro-2-methylpropyl methacrylate (n = 1.487), poly-1,1-diethylpropyl methacrylate (n = 1.489), polymethyl methacrylate (n = 1.487)
Poly (meth) acrylates such as 489) can be used. These acrylic polymers may optionally be
More than one kind may be copolymerized, and two or more kinds may be blended and used.

Further, epoxy acrylate (n = 1.48 to 1.6)
0), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1.49), polyester acrylate (n = 1.48 to 1.54) and the like can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent in terms of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether,
(Meta) such as resorcinol diglycidyl ether, diglycidyl adipic ester, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, etc. Acrylic acid adducts are mentioned. A polymer having a hydroxyl group in the molecule, such as epoxy acrylate, is effective for improving the adhesiveness. These copolymer resins can be used in combination of two or more as necessary. The softening temperature of the polymer serving as the adhesive is preferably 200 ° C. or less, more preferably 150 ° C. or less, from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C. or less, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. from the viewpoint of workability. On the other hand, it is preferable to use a polymer having a weight average molecular weight of 500 or more. When the molecular weight is 500 or less, the cohesive force of the adhesive composition is too low, and there is a possibility that the adhesiveness to the adherend is reduced. The adhesive used in the present invention may optionally contain additives such as a diluent, a plasticizer, an antioxidant, a filler, a colorant, an ultraviolet absorber, and a tackifier. The thickness of the adhesive layer is preferably 10 to 80 μm, and more than the thickness of the conductive layer is 20 to 50 μm.
It is particularly preferred that

It is preferable to use a thermosetting adhesive layer having a refractive index after curing of from 1.40 to 1.70 for use in the present invention. This is the refractive index of the plastic film and the adhesive layer used in the present invention, or the adhesive used for bonding the conductive metal to the plastic film of the plastic film with the conductive metal and the adhesive layer used in the present invention. This is because if the refractive index is different, the visible light transmittance is reduced. If the refractive index is 1.40 to 1.70, the visible light transmittance is less likely to decrease and the above-mentioned polymer has a refractive index within this range. is there.

As the conductive metal of the present invention, use is made of a metal such as copper, aluminum, nickel, iron, gold, silver, stainless steel, tungsten, chromium, titanium, or an alloy combining two or more of these metals. Can be. Copper, aluminum or nickel is suitable from the viewpoints of conductivity, circuit processing easiness, and price, and metal foil, plated metal, metal formed under vacuum such as vapor deposition is used.
The thickness of the conductive metal is preferably 0.5 to 40 μm. 40
If it exceeds μm, it is difficult to form a fine line width or the viewing angle becomes narrow. If the thickness is less than 0.5 μm, the surface resistance tends to be large, and the electromagnetic wave shielding effect tends to be poor. From the viewpoint of workability and electromagnetic wave shielding,
20 μm is more preferred.

It is preferable that the conductive metal be copper and at least the surface thereof has been subjected to a blackening treatment because the contrast is high. Further, it is possible to prevent the conductive metal from being oxidized with time and discolored. The blackening process may be performed before and after the formation of the geometrical figure. However, after the formation, the blackening process can be performed by using a method used in the field of printed wiring boards. For example, sodium chlorite (31 g / l), sodium hydroxide (15 g / l), trisodium phosphate (12 g / l)
g / l) in an aqueous solution at 95 ° C for 2 minutes. The conductive metal is nickel,
Paramagnetic metals such as iron, stainless steel and titanium are preferred because of their excellent magnetic field shielding properties. The simplest method of adhering the conductive metal to the transparent substrate is to attach the conductive metal via a thermosetting adhesive layer. If it is necessary to reduce the thickness of the conductive layer of conductive metal, a thin film such as a vacuum deposition method, a sputtering method, an ion plate method, a chemical vapor deposition method, or an electroless / electroplating method may be applied on the thermosetting adhesive layer. The conductive metal layer can be formed by combining one or more of the forming techniques. The thickness of the conductive metal is preferably 40 μm or less, and the thinner the thickness, the wider the viewing angle of the display is, which is preferable as an electromagnetic wave shielding material, and more preferably, 18 μm or less.

Geometric figures drawn with the conductive metal of the present invention include triangles such as equilateral triangles, isosceles triangles and right triangles, squares such as rectangles, rectangles, rhombuses, parallelograms, trapezoids, and (positive) hexagons. It is a pattern combining (positive) n-gons (n is a positive integer) such as square, (positive) octagon, (positive) dodecagon, (positive) octagon, etc., circle, ellipse, star, etc. ,
These units can be used alone or in combination of two or more. From the viewpoint of electromagnetic wave shielding, a triangle is most effective, but from the viewpoint of visible light transmission, if the number of (positive) n-gons is larger, the numerical aperture increases as the number of n increases. From the viewpoint, the aperture ratio is required to be 50% or more. The aperture ratio is more preferably 60% or more. The aperture ratio is a percentage of the ratio of the area obtained by subtracting the area of the conductive metal of the geometric figure drawn with the conductive metal from the effective area to the effective area of the electromagnetic wave shielding adhesive film. When the area of the display screen is defined as the effective area of the electromagnetic wave shielding adhesive film, the display screen is a visible ratio.

Further, by plating the conductive metal, the electromagnetic wave shielding property can be further improved. Either electrolytic plating or electroless plating can be used as a method for applying metal plating. The type of plating metal can be gold, silver, copper, nickel, aluminum, etc., but copper or nickel is most suitable in terms of conductivity and price. The range of plating thickness is 0.1-100μ
m is appropriate, and if it is less than 0.1 μm, the conductivity is insufficient, and there is a possibility that sufficient shielding properties may not be exhibited. If the plating thickness exceeds 100 μm, the viewing angle becomes narrow, which is not preferable. 0.5-50 μm is more preferred.

As a method of forming such a geometric figure, when a conductive metal is bonded to a transparent substrate as described above, a printing method such as a screen printing method or an intaglio offset printing method is used. After forming an etching resist pattern, there is a method of etching a conductive metal.
These methods are effective in terms of circuit processing accuracy and circuit processing efficiency. As a method of etching, there is a chemical etching method or the like. What is chemical etching?
In this method, unnecessary conductors other than the conductor portion protected by the etching resist are dissolved and removed with an etching solution. Examples of the etchant include an aqueous ferric chloride solution, an aqueous cupric chloride solution, and an alkaline etchant. Among these,
An aqueous solution of ferric chloride or cupric chloride which is low in pollution and can be reused is suitable. The concentration of the etching solution depends on the thickness of the object to be etched and the processing speed, but is usually 150 to 250.
g / liter. Further, the liquid temperature is preferably in the range of 60 to 80C. The method of exposing the object to be etched to the etching solution includes immersing the object to be etched in the etching solution,
Showering to the object to be etched in the etching solution,
For example, there is an exposure of an etching target to a gas phase of an etching agent. From the stability of etching accuracy, showering to the object to be etched in the etching solution is preferable.

The screen printing method or the intaglio offset printing method prints an etching resist ink on a conductive metal layer surface of a laminate including a transparent substrate, an adhesive, and a conductive metal layer, cures the resist, and then performs an etching process. There is a method in which a geometrical figure of a conductive metal is formed, and thereafter, the resist is removed. In screen printing, a mesh plate made by adding an emulsion to a mesh and forming the desired pattern holes in the emulsion, a meshless metal made by applying an emulsion to a meshless metal plate and forming the desired pattern holes in the emulsion. Generally, a pattern is printed using a squeegee on the conductive metal layer through a plate such as a plate.

As the etching resist ink, any one can be used as long as the cured product has resistance to the etching treatment of the conductive metal. Examples of the etching resist ink include a negative photoresist composition, a photosensitive resin composition, and a thermosetting resin composition.

Some negative-working photoresist compositions contain a resin soluble in an aqueous alkali solution, an amino resin and an acid generator. After printing and drying, the activity of ultraviolet rays, far ultraviolet rays, X-rays, electron beams, etc. Irradiation,
Further, if necessary, the composition can be cured by heating. The resin soluble in an aqueous alkali solution is not particularly limited as long as it is a resin soluble in an aqueous alkali solution, but a novolak resin obtained by condensing phenols and aldehydes is preferable. Examples of the acid generator include a halogen-containing compound, a quinonediazide compound, a sulfonic acid ester compound, and an onium salt.

In these formulations, the acid generator is preferably contained in an amount of 5 to 40 parts by weight, and the amino resin is preferably contained in an amount of 3 to 50 parts by weight based on 100 parts by weight of the aqueous alkali solution-soluble resin. The solvent is usually 200 to 20 parts by weight per 100 parts by weight of the alkali aqueous solution-soluble resin.
It is used in the range of 00 parts by weight. Examples of the solvent include ketone solvents such as acetone, diethyl ketone, methyl amyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate; and ethyl lactate. Ester solvents such as butyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methanol, ethanol, propanol, propylene glycol methyl ether, propylene glycol ethyl Alcohol solvents such as ether and propylene glycol propyl ether can be used alone or in combination of two or more.

The photosensitive resin composition includes a binder resin containing a polymerizable monomer and a photoinitiator. Examples of the binder resin include the following. Natural rubber, polyisoprene, poly-1,2-butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-2-t-butyl-
(Di) enes such as 1,3-butadiene, poly-1,3-butadiene, polyethers such as polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether, and polyvinyl butyl ether; polyvinyl acetate; Polyesters such as pionate, polyurethane, ethyl cellulose, polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, polysulfide, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, poly-t-butyl acrylate, poly -3-ethoxypropyl acrylate, polyoxycarbonyl tetramethacrylate, polymethyl acrylate, polyisopropyl methacrylate, polydodecylmethacrylate Acrylate, poly tetradecyl methacrylate, poly -n- propyl methacrylate, poly-3,3,5-trimethyl cyclohexyl methacrylate, polyethyl methacrylate, poly-2-nitro -
Poly (meth) acrylates such as 2-methylpropyl methacrylate, poly-1,1-diethylpropyl methacrylate, and polymethyl methacrylate, or copolymers thereof can be used.

As the polymerizable monomer, an acrylic monomer, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate and the like can be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesion to a support. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and allyl alcohol diacrylate. Glycidyl ether, resorcinol diglycidyl ether, diglycidyl adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, etc. (Meth) acrylic acid adducts. Polymers having a hydroxyl group in the molecule, such as epoxy acrylate, are effective for improving the adhesion to the support. These can be used by dissolving them in a general-purpose solvent or stirring and mixing with a metal dispersant or the like without using any solvent.

As the thermosetting resin, a phenol resin,
Melamine resin, epoxy resin, xylene resin and the like can be applied.
More than one kind may be copolymerized, and two or more kinds may be blended and used. These can be used usually by dissolving them in a general-purpose solvent or stirring and mixing with a metal dispersant or the like without a solvent. The photosensitive resin composition can also be used for producing a photosensitive layer when performing a microlithographic method.

These compositions used in the present invention may, if necessary, besides a dispersant, a thixotropic agent,
Additives such as an antifoaming agent, a leveling agent, a diluent, a plasticizer, an antioxidant, a metal deactivator, a coupling agent and a filler may be blended.

The line width of a geometric figure drawn with a conductive metal is preferably less than 40 μm. The line pitch is 100
It is preferable that the wire thickness is in the range of not less than μm and the wire thickness is not more than 40 μm. In addition, from the viewpoint of the invisibility of the geometric figure, the line width is 3
It is more preferably less than 0 μm, and further preferably 25 μm or less. From the viewpoint of the visible light transmittance, the line pitch is more preferably 120 μm or more and the line thickness is 18 μm or less. The line width is preferably narrower from the viewpoint of visible light transmittance as long as the line is electrically conductive. If the thickness is too small, the production tends to be difficult, so that the thickness is preferably 10 μm or more. The wire thickness is preferably set to 1 μm or more from the viewpoint of electromagnetic wave shielding properties. The larger the line pitch, the higher the aperture ratio and the higher the visible light transmittance, but the lower the electromagnetic wave shielding property. Therefore, the line pitch is preferably 1 mm or less. In addition,
If the line pitch is complicated by the combination of geometric figures,
Based on the repeating unit, the area is converted to the area of a square, and the length of one side is defined as the line pitch. The aperture ratio increases as the line interval increases, and the visible light transmittance increases. When used on the front surface of the display as described above, the aperture ratio needs to be 50% or more, but is more preferably 60% or more. If the line spacing is too large, the electromagnetic wave shielding performance is reduced, so that the line width is 1000 μm (1
mm) or less. The line interval is
When the combination is complicated by geometric figures or the like, the area is converted to the area of a square on the basis of the repeating unit, and the length of one side is set as the line interval.

The electromagnetic wave shielding adhesive film of the present invention may contain an infrared absorbing agent. Examples of the infrared absorber include metal oxides such as iron oxide, cerium oxide, tin oxide and antimony oxide, or indium-tin oxide (hereinafter, ITO), tungsten hexachloride, tin chloride, cupric sulfide, and chromium-cobalt complex salt. , Thiol-nickel complex or aminium compound, diimonium compound (trade name, manufactured by Nippon Kayaku Co., Ltd.) or anthraquinone (SIR-114), metal complex (SIR-12)
8, SIR-130, SIR-132, SIR-15
9, SIR-152, SIR-162) and organic infrared absorbers such as phthalocyanine (SIR-103) (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.), and the like.
These are preferably contained in the adhesive layer.
In addition to this, the composition dispersed in the binder resin is applied as an adhesive to a surface of an adhesive layer which flows on heating or pressure formed on a plastic film, or is directly applied to a surface of a plastic and further applied thereon. It is also possible to form an adhesive layer which flows by heating or pressurizing, or to apply it to the back surface of the film opposite to the surface of the adhesive layer formed on the plastic film. Further, a plastic film in which an infrared absorbing agent is previously contained in the plastic film can also be used. Among these infrared absorbing compounds, those having the effect of absorbing infrared rays most effectively are infrared absorbing agents such as cupric sulfide, ITO, aminium compounds, diimonium compounds and metal complexes. In the case of infrared absorbers other than organic infrared absorbers, attention must be paid to the particle size of the primary particles of these compounds. If the particle size is too large than the wavelength of infrared rays, the shielding efficiency will improve,
Diffuse reflection occurs on the particle surface, and haze increases, so that transparency decreases. On the other hand, if the particle size is too short compared to the wavelength of infrared rays, the shielding effect will be reduced. Preferred particle size is 0.01 to
0.1 to 3 μm is more preferable at 5 μm.

As an infrared absorbing agent which is an infrared absorbing material, for example, bisphenol A
Resins such as epoxy resin, bisphenol F epoxy resin, and novolak epoxy resin, diene resins such as polyisoprene, poly-1,2-butadiene, polyisobutene, and polybutene, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate , T-butyl acrylate and other polyacrylic acid ester copolymers, polyvinyl acetate, polyvinyl propionate and other polyester resins, and polyethylene, polypropylene, polystyrene, and polyolefin resins such as EVA. Is done. The optimal amount of the compound is 10
The amount of the infrared absorbent is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 0 parts by weight. 0.0
If it is less than 1 part by weight, the infrared ray shielding effect is small, and if it exceeds 10 parts by weight, transparency is impaired.

The adhesive layer containing the above-mentioned infrared absorbent in the adhesive layer is preferably formed on one surface of a plastic film, and the surface of the adhesive layer is preferably coated with a conductive metal. In addition, as described above, a composition containing an infrared absorber is formed on the surface of a plastic film, and an adhesive layer (which may or may not contain the infrared absorber) that flows on the plastic film by heating or pressing. ) May be formed, or an adhesive layer may be formed on the plastic film surface,
A composition containing an infrared absorber may be formed thereon. Further, it may be formed on the surface of the electromagnetic wave shielding adhesive film opposite to the conductive metal. Further, it may be formed on any layer of the electromagnetic wave shielding structure composed of the electromagnetic wave shielding adhesive film and the plastic plate. For example, if it is an electromagnetic shielding structure composed of one electromagnetic shielding adhesive film and one plastic plate,
It may be formed on any of the surface A of the electromagnetic wave shielding adhesive film, the surface B between the electromagnetic wave shielding adhesive film and the plastic plate, and the surface C of the plastic plate. In this case, the composition containing the infrared absorbent may be formed directly on at least one of the above-mentioned A, B and C surfaces.
At least one layer containing the infrared absorbent is required, and the other layers may not contain the infrared absorbent. It is preferable that the layer containing the infrared absorbing agent has adhesiveness, because workability and workability are easy. Specifically, it is applied to the adhesive layer surface or the back surface of the electromagnetic wave shielding adhesive film in a thickness of 0.1 to 10 μm.
The applied composition containing the infrared absorbing compound may be cured using heat or ultraviolet light. On the other hand, the infrared absorber can be used by directly mixing it with the adhesive composition of the heat-curable adhesive layer described above. In this case, the addition amount is optimally 0.01 to 5 parts by weight from the viewpoint of effect and transparency with respect to 100 parts by weight of the polymer which is a main component of the adhesive.

A thermosetting adhesive layer is obtained on the transparent base material obtained as described above, and a conductive metal layer of a geometric pattern is drawn on the adhesive layer. A peelable protective film may be laminated on the surface of the adhesive film. Such a film is appropriately selected from the above-mentioned plastic films and used. The surface of the film facing the adhesive layer may be subjected to a release treatment. As a release treatment, there is a method of applying a release agent such as a silicone polymer. Lamination of the protective film can be performed in the same manner as the above-described heating and pressing conditions. Alternatively, the protective film may be separately bonded using an adhesive. As the adhesive at this time, the above-described thermosetting adhesive or thermoplastic adhesive can be used.

An electromagnetic wave shielding adhesive film obtained as described above and having a thermosetting adhesive layer laminated on a transparent substrate, and a conductive layer of a geometric pattern drawn on the adhesive layer. May be laminated to another substrate such as a glass plate or a plastic plate to form an electromagnetic wave shield. At this time, another substrate and the electromagnetic wave shielding adhesive film of the present invention may be directly laminated and pressurized. Pressing conditions are the same as described above. Alternatively, a protective film may be separately attached to at least one of the surfaces of the other substrate and the electromagnetic wave shielding adhesive film using an adhesive. At this time, the same adhesive as described above can be used. As a bonding method at this time, a press machine or a laminator may be used. When the electromagnetic wave shielding adhesive film has a protective film, the protective film may be peeled off or peeled off and bonded as described above to form an electromagnetic wave shielding body. Further, instead of another substrate, it may be directly bonded to the display surface.

The plastic plate is a plate made of plastic, and specifically, a polystyrene resin (n = 1.5
9), acrylic resin (n = 1.46), polymethyl methacrylate resin (n = 1.49), polycarbonate resin (n = 1.58), polyvinyl chloride resin (n = 1.54), polyvinylidene chloride resin (n = 1.6
~ 1.63), polyethylene resin (n = 1.51), polypropylene resin (n = 1.50), polyamide resin (n = 1.52), polyamideimide resin (n = 1.5), polyetherimide resin (n = 1.5), polyetherketone Resin (n = 1.45), polyarylate resin (n
= 1.5-1.6), polyacetal resin (n = 1.5-1.6), thermoplastic polyester resin such as polybutylene terephthalate resin (n = 1.57), polyethylene terephthalate resin (n = 1.58), cellulose acetate resin (n = 1.49), Fluororesin (n = 1.4 ~
1.5), polysulfone resin (n = 1.63), polyethersulfone resin (n = 1.45-1.6), polymethylpentene resin (n = 1.45)
To 1.6), a thermoplastic resin and a thermosetting resin such as a polyurethane resin (n = 1.45 to 1.6) and a diallyl phthalate resin (n = 1.45 to 1.6). Among these, a polystyrene resin, an acrylic resin, a polymethyl methacrylate resin, a polycarbonate resin, a polyvinyl chloride resin, a polyethylene terephthalate resin, and a polymethyl pentene resin having excellent transparency are preferably used. The thickness of the plastic plate used in the present invention is preferably 0.5 mm to 5 mm from the viewpoint of protection of the display, strength and handling.

The electromagnetic wave shielding adhesive film of the present invention basically comprises a conductive metal having a geometric pattern, a thermosetting adhesive layer and a transparent substrate. It is preferable to use a metal foil for the conductive metal.In this case, the surface of the metal foil is often roughened in order to improve the adhesiveness.When a geometrical figure is formed, the removed metal portion is added to the adhesive layer. The roughened shape is transferred to the portion of the adhesive layer that is in contact with the metal by transferring the roughened shape, and the visible light is scattered there, so that the light transmittance is reduced and the transparency is impaired. In addition, even in plastic films, a small amount of filler is added to improve the film forming processability, imparting irregularities to the film surface, improving the slip between the films when winding the film, and improving the winding property, The surface may be subjected to a roughening treatment such as matting to improve the adhesiveness with the adhesive. As described above, the portion of the adhesive layer from which the conductive metal has been removed or the plastic film itself has irregularities intentionally for the purpose of improving adhesion, or the back shape of the conductive metal is transferred. Light is scattered on the surface and transparency is impaired, but the adhesive layer of the present invention fills the uneven surface of the plastic film and irregular reflection occurs when a resin having a refractive index close to that of the plastic film is smoothly applied to the uneven surface. Is considered to be minimized, and the transfer of the roughened shape of the conductive metal is eliminated by the flow of the adhesive layer and flows along the surface shape of the adherend. Can be Further, a geometric figure formed of a conductive material on a plastic film is not visually recognized due to a very small line width. In addition, it is considered that the line spacing is sufficiently large so that apparent transparency is exhibited. On the other hand, compared to the wavelength of the electromagnetic wave to be shielded, the line spacing of the geometrical figure is sufficiently small, and it is considered that excellent shielding properties are exhibited.

[0037]

EXAMPLES Next, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. (Example 1) <Example of preparing electromagnetic wave shielding adhesive film 1 and electromagnetic wave shielding structure 1> 50 μm thick plastic film
PET film (Toyobo Co., Ltd., trade name A-4
100, a refractive index n = 1.575), and an adhesive layer 1 containing the following infrared absorbing agent is applied to one surface thereof at room temperature using an applicator so as to have a predetermined dry coating thickness (thickness: 20 μm). Then, it was dried by heating at 90 ° C. for 5 minutes. A 12 μm thick electrolytic copper foil, which is a conductive metal, is placed through the adhesive layer 1 such that the roughened surface is on the adhesive side,
PE with copper foil, which is a plastic film with conductive metal, laminated by heating under the conditions of 10 ° C and 10 kgf / cm ²
A T film was obtained. A screen printing method [screen printing machine (LS-34G with alignment device, manufactured by Neurong Seimitsu Co., Ltd.)
X), meshless metal plate made of nickel alloy (manufactured by Mesh Kogyo Co., Ltd., thickness 50 μm, pattern size 8 mm ×
8mm) and a Permalex metal squeegee (Tomo Kogyo Co., Ltd. imported product)], etching resist (trade name, manufactured by Hitachi Chemical Co., Ltd., RAYCA) on a copper thin film.
ST), using a line width of 40 μm and a line interval of 250
A μm etching resist pattern was formed. Thereafter, a 200 g / liter ferric chloride aqueous solution (liquid temperature 60
C.) for 3 minutes and chemical etching (etching rate 2.0 mm / min) to form a copper grid pattern having a line width of 25 μm and a line interval of 250 μm on the PET film, to obtain an electromagnetic wave shielding adhesive film 1. The visible light transmittance of this electromagnetic wave shielding adhesive film 1 is 20%.
It was below. An adhesive layer was formed on the release surface of a 50 μm-thick PET film (release coating PET manufactured by Tosello Co., Ltd.) in which one surface of the electromagnetic wave shielding adhesive film 1 was peeled off as a protective film using a hot press machine. 110 ℃, 20Kgf / c
The film was heated and pressed under the conditions of m ² and 15 minutes to obtain an electromagnetic wave shielding film. The protective film of the electromagnetic wave shielding adhesive film 1 thus produced was peeled off, and a commercially available acrylic plate (como glass; trade name, manufactured by Kuraray Co., Ltd., 3 m thick)
(m, n = 1.49) so as to be in contact with the surface on which the adhesive layer was formed, and heat-pressed at 110 ° C., 20 kg / cm ^{2 for} 15 minutes to obtain an electromagnetic wave shielding component 1.

<Composition of Adhesive Layer 1> 100 parts by weight of Byron 200 (manufactured by Toyobo Co., Ltd .; saturated polyester resin, Mn = 20,000) SIR-159 (infrared absorbent 1: manufactured by Mitsui Toatsu Chemicals, Inc.) Trade name, metal complex) 0.5 parts by weight Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., aliphatic trifunctional isocyanate) 5 parts by weight Toluene 450 parts by weight Ethyl acetate 10 parts by weight Adhesive layer 1 described above The refractive index of the composition after the solvent was dried and cured was 1.54, and the degree of curing of the DSC before curing (after lamination) was 10%.

Example 2 <Example of Producing Electromagnetic Wave Shielding Adhesive Film 2 and Electromagnetic Wave Shielding Component 2> An adhesive layer 2 containing the following infrared absorbing agent was applied to one side of a 25 μm-thick PET film at room temperature using an applicator. And dried by heating at 90 ° C. for 5 minutes. An aluminum foil having a thickness of 25 μm is laminated by heating (100 ° C., 10 kgf / c) through the adhesive layer 2 (40 μm in thickness).
m ² ) and adhered to obtain a PET film with an aluminum foil. An etching resist pattern having a line width of 40 μm and a line interval of 125 μm was formed on the PET film with the aluminum foil by the same screen printing method as in Example 1. Thereafter, a 200 g / liter ferric chloride aqueous solution (liquid temperature: 60 ° C.) was sprayed and subjected to chemical etching to form an aluminum grid pattern having a line width of 15 μm and a line interval of 125 μm on the PET film. The visible light transmittance of this electromagnetic wave shielding adhesive film 2 was 20% or less. This electromagnetic wave shielding adhesive film 1 was heat-pressed to a thickness of 5 on the same side as in Example 1 with one surface peeled off.
120 μm so that the surface on which the adhesive layer is formed is in contact with the release surface of the PET film (protective film) of 0 μm.
The film was heat-pressed using a hot press at 30 ° C., 30 Kgf / cm ² and 30 minutes to obtain an electromagnetic wave shielding adhesive film 2. The protective film of the electromagnetic wave shielding adhesive film 2 thus produced was peeled off, and a commercially available acrylic plate (como glass; trade name, manufactured by Kuraray Co., Ltd., thickness: 3 mm)
12 so that the surface on which the adhesive layer is formed is in contact with
It was heated and pressed using a hot press under the conditions of 0 ° C., 30 kgf / cm ² , and 30 minutes to obtain an electromagnetic wave shielding component 2.

<Composition of Adhesive Layer 2> VM-D Medium (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd .; terpolymer of vinyl chloride / vinyl acetate / acrylic acid) 100 parts by weight UFP-HX (infrared ray) Absorbent 2: trade name, manufactured by Sumitomo Metal Mining Co., Ltd .; ITO, average particle size: 0.1 μm) 0.4 parts by weight Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., aliphatic trifunctional isocyanate) 5 parts by weight MEK 330 parts by weight Cyclohexanone 15 parts by weight The refractive index of the composition for the adhesive layer 2 after solvent drying and curing was 1.51, and the degree of curing (after lamination) of the DSC before curing was 15%.

Example 3 <Example of Producing Electromagnetic Shielding Adhesive Film 3 and Electromagnetic Shielding Construct 3> PET film with copper foil similar to that of Example 1 (however, the following adhesive layer 3 was used as the adhesive. An intaglio offset printing machine [glass plate; soda lime glass, average depth of groove 10 μm] on a copper foil having a thickness of 5 μm).
m, average internal surface roughness 1 μm, thickness of silicone polymer release layer 0.5 μm-blanket; made of epoxy-modified silicone rubber, hardness 50 according to JIS K 6253
Degree, average surface roughness (Rz) 0.5 μm] to obtain an etching resist (trade name, R, manufactured by Hitachi Chemical Co., Ltd.)
(AYCAST), an etching resist pattern having a line width of 30 μm and a line interval of 250 μm was prepared. Thereafter, a copper lattice pattern was formed on the adhesive layer 3 by the same chemical etching as in Example 1. Using a roll laminator, the same surface as in Example 1 was peeled off, and the surface on which the adhesive layer was formed was in contact with the peeled surface of a PET film (protective film) having a thickness of 50 μm (protective film) at 110 ° C. and 20 kgf. The film was heated and press-bonded under the condition of / cm ² to produce an electromagnetic wave shielding adhesive film 3.
The visible light transmittance of the adhesive film 3 was 20% or less. Thereafter, the protective film of the electromagnetic wave shielding adhesive film 3 is peeled off, and the surface on which the adhesive layer is formed is in contact with a commercially available acrylic plate (como glass, trade name, manufactured by Kuraray Co., Ltd., thickness: 3 mm) using a roll laminator. Then, it was heated and pressed under the conditions of 110 ° C. and 20 kgf / cm ² to obtain an electromagnetic wave shielding component 3. <Composition of Adhesive Layer 3> S-1005 (trade name, manufactured by Toa Gosei Chemical Co., Ltd .; acrylic resin) 100 parts by weight IRG-002 (infrared absorbent 3: trade name, manufactured by Nippon Kayaku Co., Ltd .; aminium-based Compound) 1.2 parts by weight Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., aliphatic trifunctional isocyanate) 5 parts by weight MEK 285 parts by weight Cyclohexanone 5 parts by weight Solvent of the composition of the above adhesive layer 3 The refractive index after drying and curing was 1.50, and the degree of curing of the DSC before curing (before lamination) was 5%.

(Example 4) An electromagnetic wave shielding property obtained in the same manner as in Example 1 by using the following composition of the adhesive layer 4 so that the thickness of the dried adhesive layer 4 was 20 μm. As the adhesive film 4, an electromagnetic wave shielding component 4 was produced from the electromagnetic wave shielding adhesive film 4 and a plastic plate. <Composition of Adhesive Layer 4> 100 parts by weight of Vistanex MML-140 (trade name of Tonex Corporation; polyisobutylene) IRG-002 (infrared absorbent 3: trade name of Nippon Kayaku Co., Ltd .; aminium compound 1.2 parts by weight Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by weight MEK 285 parts by weight Cyclohexanone 5 parts by weight The refractive index of the composition of the adhesive layer 4 after solvent drying and curing is 1.45. The degree of curing by DSC before curing (after lamination) was 3%.

(Example 5) An electromagnetic wave shielding property obtained in the same manner as in Example 1 by using the following composition of the adhesive layer 5 so that the thickness of the dried adhesive layer 5 was 20 μm. As the adhesive film 5, an electromagnetic wave shielding component 5 was produced from the electromagnetic wave shielding adhesive film 5 and a plastic plate. <Composition of Adhesive Layer 5> VR-103 (trade name, manufactured by Mitsui DuPont Polychemicals, Inc .; maleic anhydride-modified EVA, vinyl acetate modification ratio 30% by weight) 100 parts by weight IRG-002 (infrared absorbent 3 : Nippon Kayaku Co., Ltd .; aminium compound) 1.2 parts by weight Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., aliphatic trifunctional isocyanate) 5 parts by weight MEK 285 parts by weight cyclohexanone 5 Part by weight The refractive index of the composition of the adhesive layer 5 after drying and curing in a solvent was 1.47, and the degree of curing (after lamination) by DSC before curing was 10%.

(Example 6) An electromagnetic wave shielding property obtained in the same manner as in Example 1 by using the following composition for the adhesive layer 6 so that the thickness of the adhesive layer 6 after drying was 20 μm. As the adhesive film 6, an electromagnetic wave shielding component 6 was produced from the electromagnetic wave shielding adhesive film 6 and a plastic plate. <Composition of Adhesive Layer 6> Epicoat YL-983U (trade name, manufactured by Yuka Shell Epoxy Co., Ltd .; bisphenol F-type epoxy resin, epoxy equivalent 170) 100 parts by weight SIR-159 (infrared absorbent 1: Mitsui Higashi) 0.5 parts by weight Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., aliphatic trifunctional isocyanate) 5 parts by weight Toluene 450 parts by weight Ethyl acetate 10 parts by weight Adhesive layer 6 described above The composition (1) had a refractive index of 1.49 after solvent drying and curing, and the degree of curing (after lamination) by DSC before curing was 5%.

Example 7 A plastic film was made of PE
T (50 μm) to polycarbonate film (50 μm)
m, n = 1.58), except that the thickness of the adhesive layer was changed from 20 μm to 30 μm, to obtain an electromagnetic wave shielding adhesive film 7 and an electromagnetic wave shielding structure 7 in the same manner as in Example 2.

(Embodiment 8) The line width is changed from 10 μm to 30
The electromagnetic wave shielding adhesive film 8 and the electromagnetic wave shielding structure 8 were obtained in the same manner as in Example 3 except that the line spacing was changed from 100 μm to 500 μm, and the thickness of the adhesive layer was changed from 5 μm to 10 μm.

Example 9 Example 1 was repeated except that the copper lattice pattern formed on the PET film was blackened.
In the same manner as in the above, an electromagnetic wave shielding adhesive film 9 and an electromagnetic wave shielding structure 9 were obtained.

Example 10 <Example of Producing Electromagnetic Wave Shielding Adhesive Film 10 and Electromagnetic Wave Shielding Constructing Body 10> A plastic film having a thickness of 5
Using a 0 μm polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., trade name A-4100, refractive index n = 1.575), the adhesive layer 1 of Example 1 (provided that an infrared absorbent Not included) at room temperature using an applicator to a predetermined dry coating thickness,
It was dried by heating at 90 ° C. for 20 minutes. An electrolytic copper foil having a thickness of 12 μm, which is a conductive metal, is placed through the adhesive layer 1 at 180 ° C. and 30 ° C. so that the roughened surface is on the adhesive layer side.
Heat lamination was performed under the conditions of Kgf / cm ² to obtain a PET film with a copper foil, which is a plastic film with a conductive metal. An etching resist pattern having a line width of 40 μm and a line interval of 250 μm was formed on the copper foil of the obtained PET film with copper foil by using a screen printing method according to Example 1. Thereafter, a line width of 25 μm was formed by a chemical etching method using an aqueous ferric chloride solution.
A copper lattice pattern having a length of 250 m and a line interval of 250 μm was formed on the PET film, and an electromagnetic wave shielding adhesive film 1 was obtained. The visible light transmittance of the adhesive film 1 was 20% or less. The surface on which the adhesive layer is formed is in contact with the release surface of a 50 μm-thick PET film (protective film) obtained by subjecting this electromagnetic wave shielding adhesive film 1 to a 50 μm-thick PET film (protective film) obtained by performing a release treatment on one side in the same manner as in Example 1 using a hot press. The film was heated and pressed at 110 ° C., 20 kgf / cm ² and 15 minutes to obtain an electromagnetic wave shielding film 10. The protective film of the electromagnetic wave shielding adhesive film 10 thus produced was peeled off, and a commercially available acrylic plate (como glass; trade name, manufactured by Kuraray Co., Ltd., thickness: 3 mm,
n = 1.49), 110 ° C., 20 kgf / cm ² , 15
The sheets were bonded together by heating and pressing under the conditions of minutes.

(Comparative Example 1) 0.1 μm as conductive material
(1,000 °) A composition obtained by removing the infrared absorbent directly from the composition of the adhesive layer 1 without forming a pattern using ITO vapor-deposited PET deposited on the entire surface, and obtained in the same manner as in Example 1. An electromagnetic wave shielding structure was manufactured.

The aperture ratio, electromagnetic wave shielding property, visible light transmittance, invisibility, infrared ray shielding rate and electromagnetic wave of a geometrical figure drawn with a conductive metal material of the electromagnetic wave shielding adhesive film obtained as described above. The adhesive properties of the shield before and after the heat treatment were measured. The results are shown in Table 1.

The refractive index of the composition in the adhesive layer was measured with a refractometer (Abago Refractometer, manufactured by Atago Optical Machine Works). The aperture ratio of a geometric figure drawn with a conductive metal was measured based on a micrograph. DSC was measured by a differential scanning calorimeter (Dupont Model 910-DSC) at a heating rate of 10 ° C.
° C / min, measured from room temperature (25 ° C) to 200 ° C. The electromagnetic wave shielding property is measured by inserting a sample between flanges of a coaxial waveguide converter (manufactured by Japan High Frequency Corporation, TWC-S-024) and using a spectrum analyzer (YHP, 8510B).
Frequency 3 using a vector network analyzer)
The measurement was performed at 0 MHz to 1 GHz. The measurement of visible light transmittance is performed using a double beam spectrophotometer (manufactured by Hitachi, Ltd.
(200-10 type), and the average value of the transmittance at 400 to 700 nm was used. The non-visibility is evaluated by observing the electromagnetic wave shielding structure in which the electromagnetic wave shielding adhesive film is attached to the acrylic plate from a place 0.5 m away, and by recognizing the geometric figure formed of the conductive metal. Those that could not be recognized were evaluated as good, and those that could be recognized were evaluated as NG.
The infrared shielding rate is measured by a spectrophotometer (manufactured by Hitachi, Ltd.
U-3410), the average value of infrared absorptance in the region of 900 to 1,100 nm was used. The adhesive force was measured by a tensile tester (Tensilon U manufactured by Toyo Baldwin Co., Ltd.).
Using TM-4-100), the measurement was performed at a width of 10 mm, a direction of 90 °, and a peeling speed of 50 mm / min.

[0052]

[Table 1]

Comparative Example 1, in which ITO (indium-tin oxide) was deposited on a PET film, was inferior in electromagnetic wave shielding properties. It has a geometrical figure drawn with a conductive metal as shown in the embodiment of the present invention and has an aperture ratio of 50.
% Or more, a thermosetting adhesive layer is used as the adhesive layer, the degree of curing is less than 60%, and the refractive index after curing is 1.40 to
In the range of 1.70, the thickness of the adhesive layer was equal to or larger than the thickness of the conductive metal, and the adhesive layer containing the infrared absorbent showed a preferable value. Also, the line width drawn with the conductive metal is 40 μm or less, and the line interval is 100 μm.
m and a conductive metal having a line thickness of 40 μm or less showed preferable values. In addition, the electromagnetic wave shielding structure in which copper was blackened as described in Example 9 was able to comfortably appreciate a clear image with a large contrast.

[0054]

As is clear from the examples, the electromagnetic wave shielding adhesive film obtained by the present invention can be easily adhered to an adherend and used, and since it has excellent adhesion, there is no electromagnetic wave leakage and the shielding function. Is particularly good. In addition, optical characteristics such as visible light transmittance and invisibility are good, and there is little change in adhesive characteristics at a high temperature over a long period of time, so that an excellent electromagnetic shielding adhesive film can be provided. Since the electromagnetic wave shielding adhesive film and the electromagnetic wave shielding structure of the present invention are excellent in electromagnetic wave shielding properties and transparency, in addition to a display, a measuring device, a measuring device, and a manufacturing device for generating or protecting from electromagnetic waves It can be used by providing it in windows and housings, especially windows such as windows where transparency is required. The display according to the present invention has a small electromagnetic wave leakage, is lightweight, compact, has excellent transparency, has a large visible light transmittance, and has good non-visibility.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Minoru Tosaka 1500 Oji Ogawa, Shimodate-shi, Ibaraki F-term in Shimodate Research Laboratory, Hitachi Chemical Co., Ltd. BA03 BA04 BA07 BA10A BA10C BA10D BA25 CA02B CA30B EC182 EJ08B EJ15C EJ152 EJ64C EJ91 GB41 HB00 HB31C HB312 JB13B JD08 JG01C JG06C JK06 JL11B JN01 JN01A JN08 JN18B YY00B 5E321 AA04 BB23 BB25 CC16 GG05 GH01 5G435 AA00 AA16 AA18 BB06 FF01 GG11 GG33 HH02 HH12 KK07

Claims (15)

[Claims] An etching resist pattern produced by a screen printing method or an offset printing method in a plastic film with a conductive metal in which a conductive metal layer is laminated on a transparent substrate via a thermosetting adhesive layer. A method for producing an electromagnetic wave shielding adhesive film, comprising forming a geometrical figure made of a conductive metal by forming and etching a conductive metal layer. 2. The method for producing an electromagnetic wave shielding adhesive film according to claim 1, wherein the degree of curing of the thermosetting adhesive layer is less than 60%. 3. The thermosetting adhesive layer has a refractive index of 60.
The method for producing an electromagnetic wave shielding adhesive film according to claim 1 or 2, wherein the percentage is not less than 1.40 and 1.70. 4. The method for producing an electromagnetic wave shielding adhesive film according to claim 1, wherein the thickness of the thermosetting adhesive layer is not less than the thickness of the conductive metal. 5. The method for producing an electromagnetic wave shielding adhesive film according to claim 1, wherein an infrared absorbing agent is contained in the thermosetting adhesive layer. 6. The electromagnetic wave shielding property according to claim 1, wherein a line width of the geometrical figure drawn by the conductive metal is 40 μm or less, a line interval is 100 μm or more, and a line thickness is 40 μm or less. Manufacturing method of adhesive film. 7. The method for producing an electromagnetic wave shielding adhesive film according to claim 1, wherein the metal of the plastic film with a conductive metal is copper, aluminum or nickel having a thickness of 0.5 to 40 μm. 8. The plastic film of the plastic film with a conductive metal is a polyethylene terephthalate film or a polycarbonate film.
8. The method for producing an electromagnetic wave shielding adhesive film according to any one of items 1 to 7. 9. The method according to claim 1, wherein the conductive metal is copper, and at least the surface thereof is blackened.
9. The method for producing an electromagnetic wave shielding adhesive film according to any one of 8. 10. The method for producing an electromagnetic wave shielding adhesive film according to claim 1, wherein the conductive metal is a paramagnetic metal. 11. A peelable protective film is laminated on the side opposite to the transparent substrate simultaneously with or after the pressing.
11. The method for producing an electromagnetic wave shielding adhesive film according to any one of items 10 to 10. 12. An electromagnetic wave obtained by performing the method for producing an electromagnetic wave shielding adhesive film according to any one of claims 1 to 11, and then bonding the obtained electromagnetic wave shielding adhesive film to a plastic plate. Manufacturing method of the shielding structure. 13. The method for producing an electromagnetic wave shielding adhesive film according to claim 12, wherein the protective film of the obtained electromagnetic wave shielding adhesive film is peeled or peeled, and then a plastic plate is laminated. A method for producing an electromagnetic wave shielding component. 14. The electromagnetic wave shielding adhesive film according to claim 1, wherein the obtained electromagnetic wave shielding adhesive film is bonded to a display surface. Manufacturing method of shielded display. 15. After performing the method for producing an electromagnetic wave shielding adhesive film according to claim 12, the protective film of the obtained electromagnetic wave shielding adhesive film is peeled or peeled off, and then bonded to a display surface. A method for producing an electromagnetic wave shielding display, comprising: