JP2007027389A - Electromagnetic wave shield filter, its production method, display equipped therewith and electromagnetic wave shield structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To economically provide an electromagnetic wave shield filter which has a predetermined electromagnetic wave shield performance, a good optical characteristic and an excellent durability. <P>SOLUTION: A transparent electromagnetic wave shield filter 1 has a stopper layer 3, an adhesive layer 4, and a conductor layer 5 on a transparent substrate 2. The adhesive layer 4 is not formed in the opening of the conductor layer 5. In manufacturing the electromagnetic wave shield filter, a composite body is prepared in which the stopper layer 3, the adhesive layer 4 and the conductor layer 5 having the opening are formed on the transparent substrate 2, and in the composite body, the adhesive layer 4 is removed in the opening of the conductor layer 5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electromagnetic wave shielding filter having shielding properties and transparency of electromagnetic waves generated from a display using, for example, a cathode ray tube (CRT), plasma (PDP), liquid crystal, electroluminescence (EL), and the like, and the filter The present invention relates to a display and an electromagnetic wave shielding structure.

  In recent years, as the use of various electrical equipment and electronic application equipment has increased, electromagnetic noise interference (EMI) has been increasing. Noise is roughly divided into conduction noise and radiation noise. As a countermeasure against such conduction noise, there is a method using a noise filter or the like. On the other hand, as measures against radiation noise, it is necessary to insulate the space electromagnetically, so the case is made of a metal body or a high conductor, or a metal plate is inserted between the circuit board and the circuit board, Methods such as wrapping cables with metal foil are used. These methods can be expected to have an EMI shielding effect on a circuit or a power supply block, but are not necessarily suitable for EMI shielding applications generated from the front surface of a display such as a CRT or PDP because they are opaque.

As a method for achieving both EMI shielding properties and transparency, a method of forming a thin film conductive layer by vapor-depositing a metal or metal oxide on a transparent substrate (JP-A-1-278800, JP-A-5-323101). Have been proposed). On the other hand, an EMI shielding material (see JP-A-5-327274 and JP-A-5-269912) in which good conductive fibers are embedded in a transparent base material or conductive resin containing metal powder or the like is directly printed on a transparent substrate. An EMI shielding material (see Japanese Patent Application Laid-Open Nos. 62-57297 and 2-52499), and further, a transparent resin layer is formed on a transparent substrate such as polycarbonate having a thickness of about 2 mm, A shielding material (see Japanese Patent Laid-Open No. 5-283889) in which a copper mesh pattern is formed by an electroless plating method has been proposed. Further, a shielding material having a configuration in which a metal foil and a resin layer are laminated on a transparent substrate via an adhesive layer (see JP-A-10-41682 and JP-A-2003-152385) has been proposed.
JP-A-1-278800 JP-A-5-323101 JP-A-5-327274 Japanese Patent Laid-Open No. 5-269912 JP 62-57297 A JP-A-2-52499 Japanese Patent Laid-Open No. 5-288989 Japanese Patent Laid-Open No. 10-41682 JP 2003-152385 A

  As a method for achieving both EMI shielding properties and transparency, a thin film conductive layer is formed by depositing a metal or a metal oxide on the transparent base material disclosed in the above-mentioned JP-A-1-278800 and JP-A-5-323101. The method of forming the layer is 20 dB or less for the shielding effect of 30 dB or more required at 1 GHz because the surface resistance of the conductive layer becomes too large when the film thickness is sufficient to achieve transparency (several hundred to 2000 mm). And it was insufficient.

  In the EMI shield material (Japanese Patent Laid-Open No. 5-327274 and Japanese Patent Laid-Open No. 5-269912) in which the highly conductive fiber is embedded in the transparent base material, the 1 GHz EMI shield effect is sufficiently large as 40 to 50 dB, In order to prevent the conductive fibers from being regularly arranged, the fiber diameter is too thick as 35 μm, so that the fibers are visible (hereinafter referred to as visibility) and are not suitable for display applications.

  Similarly, in the case of an EMI shielding material in which a conductive resin containing metal powder or the like disclosed in JP-A-62-57297 and JP-A-2-52499 is directly printed on a transparent substrate, a line is also formed due to the limit of printing accuracy. The width was about 100 μm, and visibility was developed, which was not suitable. Furthermore, in 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 described in JP-A-5-283890, and a copper mesh pattern is formed thereon by an electroless plating method, In order to ensure the adhesion of electroless plating, it is necessary to roughen the surface of the transparent substrate. As this roughening means, generally a highly toxic oxidizing agent such as chromic acid or permanganic acid must be used, and this method has been difficult to achieve satisfactory roughening with resins other than ABS. . Even if EMI shielding properties and transparency can be achieved by this method, it is difficult to reduce the thickness of the transparent substrate, which is not suitable for film formation.

  In general, when the transparent substrate is thick, it cannot be brought into close contact with the display, so that electromagnetic wave leakage from the display becomes large. In addition, in terms of manufacturing, there are also disadvantages that the shield material cannot be made into a scroll or the like and thus becomes bulky and is not suitable for automation, resulting in increased manufacturing costs.

  Shielding properties of electromagnetic waves generated from the front of the display not only have an EMI shielding function of 30 dB or more at 1 GHz, but also have good visible light transmittance and high visible light transmittance, and also prevent leakage of electromagnetic waves. The non-visibility, which is a property in which the adhesiveness adhered to the surface and a shield material cannot be visually confirmed, is required. As for adhesiveness, it is necessary to easily stick to glass or general-purpose polymer plates at a relatively low temperature and to have good adhesion over a long period of time. However, a material satisfying these characteristics has not been obtained.

  Furthermore, the shielding material having a structure in which a metal foil and a resin layer are laminated on a transparent substrate via an adhesive layer, as disclosed in JP-A-10-41682 and JP-A-2003-152385, has a visible light transmittance. In order to increase the transparency of the adhesive layer itself, the difference in refractive index between the adhesive layer and the resin layer must be 0.14 or less, and there is a limitation in the selection of the adhesive or the resin material. There was a problem that the optimum material could not be selected.

  Therefore, the present inventors proposed a process for removing the adhesive layer by etching or physical removal according to Japanese Patent Application No. 2005-162700. However, this method still has room for improvement in the efficiency and uniformity of the removal operation when the adhesive layer to be removed has a large area.

  In view of such points, the present invention provides an electromagnetic wave shielding filter having EMI shielding properties and transparency, invisibility and good characteristics, and an electromagnetic shielding filter having transparency, and an adhesive layer for the purpose of improving light transmittance. Is provided with high uniformity, and a display filter having extremely high transparency and excellent electromagnetic shielding properties is provided.

  In order to solve the above problems, an electromagnetic wave shielding filter according to the present invention is an electromagnetic wave shielding filter having transparency, on a transparent substrate, a stopper layer, an adhesive layer, and a conductor layer having an opening, And the adhesive layer is not formed in the opening of the conductor layer.

  In such an electromagnetic wave shielding filter according to the present invention, a transparent resin layer can be further formed at least in the opening of the conductor layer.

  Moreover, the manufacturing method of the electromagnetic wave shielding filter according to the present invention is the above manufacturing method of the electromagnetic wave shielding filter, in which a stopper layer, an adhesive layer, and a conductor layer having an opening are formed on a transparent substrate. The composite is prepared, and then the composite is subjected to an adhesive layer removal treatment comprising removing the adhesive layer in the opening of the mesh layer.

  And the display by this invention is characterized by the above-mentioned electromagnetic wave shielding filter being arrange | positioned at the observer side of the display.

  Moreover, the electromagnetic wave shield structure by this invention comprises said electromagnetic wave shield filter, It is characterized by the above-mentioned.

  The electromagnetic wave shielding filter according to the present invention preferably includes any one of the following aspects.

(1) When the stopper layer and the adhesive layer are subjected to an adhesive layer removal treatment under the same conditions, the removal rate of the stopper layer is ½ or less of the removal rate of the adhesive layer. Electromagnetic shield filter.

(2) The electromagnetic wave shielding filter, wherein the stopper layer is transparent.

(3) The electromagnetic wave shielding filter, wherein the stopper layer is any one of an inorganic oxide film, an inorganic nitride film, an inorganic carbon film, an inorganic oxynitride film, an inorganic oxycarbide film, and an inorganic oxynitride carbon film.

(4) The above-mentioned stopper layer is an inorganic oxide or inorganic nitride of an inorganic element selected from the group consisting of silicon, aluminum, chromium, magnesium, calcium, titanium, niobium, molybdenum, tantalum, indium, tin and zirconium An electromagnetic wave shielding filter comprising any one of inorganic carbide, inorganic oxide carbide, inorganic oxynitride, inorganic carbonitride, and inorganic oxycarbonitride.

(5) The electromagnetic wave shielding filter, wherein the stopper layer has a thickness of 5 nm to 100 μm.

(6) The electromagnetic wave shielding filter, wherein the stopper layer has a surface average roughness Ra of 50 nm or less.

(7) The electromagnetic wave shielding filter, wherein the stopper layer has a maximum surface height difference PV of 500 nm or less.

(8) The electromagnetic wave shielding filter, wherein the stopper layer has a refractive index difference of 0.15 or less with respect to the transparent substrate.

(9) The electromagnetic wave shielding filter, wherein the stopper layer has a refractive index difference of 0.15 or more with respect to the transparent substrate.

(10) An electromagnetic wave shielding filter in which a difference in refractive index between the transparent substrate and the transparent resin layer is 0.14 or less.

(11) The electromagnetic wave shielding filter, wherein the transparent resin layer has adhesiveness.

(12) The electromagnetic wave shielding filter, wherein the transparent substrate has an uneven surface formed on the surface on the stopper layer side.

(13) The conductor layer having the opening is formed by a chemical etching process in which a geometrical figure-shaped opening is formed, the line width is 40 μm or less, the line interval is 200 μm or more, and the line thickness is 40 μm or less. There is an electromagnetic shielding filter.

(14) The electromagnetic wave shielding filter, wherein the conductor layer having the opening is copper whose surface is at least blackened.

(15) An electromagnetic wave shielding filter in which the conductor layer having the opening is a paramagnetic metal.

(16) The transparent substrate is a polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, cyclic polyolefin resin film, norbornene resin film, epoxy (meth) acrylate resin film, urethane (meth) acrylate resin film, (meth) An electromagnetic wave shielding filter, which is either an acrylate resin film or a polyorganosilsesquioxane-containing silicone resin film.

(17) The stopper layer is formed by vapor deposition, sputtering, ion plating, ion plating using a pressure gradient plasma gun, plasma CVD, hot wire CVD, atmospheric pressure plasma CVD, surface wave. An electromagnetic wave shielding filter formed by any one of plasma CVD methods.

(18) An electromagnetic wave shielding filter in which the stopper layer is formed by a sol-gel method.

(19) An electromagnetic wave shielding filter in which the stopper layer is formed by a spray pyrolysis method.

(20) An electromagnetic wave shielding filter in which the stopper layer is formed by a chemical solution phase method.

  And the manufacturing method of the electromagnetic wave shield filter according to the present invention preferably includes any one of the following aspects.

(1) A method for manufacturing an electromagnetic wave shielding filter, wherein the composite is prepared by bonding a transparent substrate having a stopper layer and a conductor layer having an opening coated with an adhesive.

(2) Furthermore, the manufacturing method of the electromagnetic wave shield filter which removes the adhesive bond layer in the opening part of the said conductor layer by attaching | subjecting the adhesive bond layer removal process from the said conductor layer surface side.

(3) After the transparent base material having the stopper layer and the conductor layer are joined with an adhesive, the composite is prepared by subjecting this to a chemical etching treatment to form an opening in the conductor layer. Then, the manufacturing method of the electromagnetic wave shield filter which removes the adhesive bond layer in the opening part of the said conductor layer by giving to an adhesive bond layer removal process from the said conductor layer surface side.

(4) The transparent base material having a stopper layer and the conductor layer having an opening are bonded by an adhesive to prepare the composite, and then the adhesive layer in the opening of the conductor layer, The manufacturing method of the electromagnetic wave shield filter removed by attaching | subjecting to an adhesive bond layer removal process from the said conductor layer surface side.

(5) The adhesive layer removal treatment is performed by (1) plasma etching method, (2) reactive plasma etching method, (3) reactive etching method, (4) photoetching method (5) polishing method, (6 ) Sand blasting, (7) Dry ice blasting, (8) High pressure fluid removal method (9) Flame treatment (10) Corona treatment (11) Ozone treatment (12) Includes at least one of photophysographic methods The manufacturing method of an electromagnetic wave shield filter.

  The electromagnetic wave shielding filter according to the present invention is an electromagnetic wave shielding filter having transparency, wherein a stopper layer, an adhesive layer, and a conductor layer having an opening are formed on a transparent substrate, and Since the adhesive layer is formed only in the opening of the conductor layer, the light transmittance in the opening of the conductor layer is particularly excellent. Therefore, when arranged on the front surface of the display, electromagnetic waves can be shielded while maintaining the display quality of the display.

  In the electromagnetic wave shielding filter of the present invention, a wide range of adhesives can be used because the adhesive layer does not need to be highly transparent. Therefore, it is possible to use an adhesive that could not be used from the viewpoint of transparency and the like, and an optimal adhesive according to a specific application can be used. A shield filter can be easily obtained. In the present invention, in some cases, for example, an opaque adhesive having a light transmittance of 70% or less or a colored adhesive can be used.

  Further, by using an appropriate adhesive, sufficient adhesive strength can be obtained even if the thickness of the adhesive layer is made thinner than before, so that the weight and thickness of the electromagnetic wave shielding filter can be reduced, and Manufacturing cost can be suppressed.

  In the case where a transparent resin layer is further formed at least in the opening of the conductor layer, it is not necessary to make the refractive index of the adhesive layer and this transparent resin layer the same or approximate. Transparent resin materials that are inappropriate from the viewpoint can also be used in the present invention. Therefore, the weight, thinness, and manufacturing cost of the electromagnetic wave shielding filter can be further reduced.

  Since a general adhesive is composed of a mixture of a plurality of components, and the adhesive is usually diluted with a solvent or the like when forming the adhesive layer, each of these components is another component of the electromagnetic shielding filter. Acting on the material (for example, transparent resin layer formed in the opening of the conductor layer, transparent base material, colored layer, etc.) to alter or deteriorate the above other constituent materials, The adhesive layer may be deteriorated depending on the constituent material, and the light transmittance of the opening of the conductor layer may be lowered, or the adhesive strength may be significantly reduced. However, in the electromagnetic wave shielding filter according to the present invention, since the amount of the adhesive and the surface area are significantly smaller than those of the conventional one, the reduction of the light transmission or the coloration due to the alteration or the deterioration of the adhesive strength, etc. at the opening of the conductor layer is effective. Therefore, light transmission and durability are remarkably improved.

  Furthermore, in the electromagnetic wave shielding filter according to the present invention, since the stopper layer is formed as the lower layer of the adhesive layer (that is, the layer on the transparent base material side of the adhesive layer), the transparent base material layer is subjected to the adhesive layer removal treatment. Will not be exposed. This effectively prevents the characteristics of the transparent base layer, particularly the surface characteristics and optical characteristics, from changing due to the adhesive layer removal treatment.

  And since this stopper layer exists, the characteristic change of a transparent base material layer is effectively prevented as mentioned above, Therefore The optimal conditions and tolerance | permissible_range of an adhesive bond layer removal process are expanded (broadening). . Thereby, the removal process of an adhesive bond layer can be performed efficiently, uniformly and reliably. This effect is particularly noticeable when manufacturing a large electromagnetic shield filter.

  Since this stopper layer has high resistance to the adhesive layer removing process, the deterioration of the characteristics of the stopper layer exposed in the adhesive layer removing process is prevented. Therefore, according to the present invention, an electromagnetic wave shielding filter having excellent optical characteristics such as transparency is provided.

The present invention is described in detail below.
FIG. 1 is a cross-sectional view illustrating a basic form example of an electromagnetic wave shielding filter according to the present invention.

  The electromagnetic wave shielding filter 1 according to the present invention shown in FIG. 1 is the most basic form, and a transparent layer 2 has a stopper layer 3, an adhesive layer 4, and a conductor layer 5 having an opening. It is formed, and the adhesive layer 4 is not formed in the opening 5X of the conductor layer 5. In addition, the structure which consists of the transparent base material 2, the stopper layer 3, the adhesive bond layer 4, and the conductor layer 5 which has an opening part may be called "composite" in this specification.

  In such an electromagnetic wave shielding filter 1 according to the present invention, preferably, a transparent resin layer 6 can be further formed in at least the opening 5X of the conductor layer 5. As shown in FIG. 1, the transparent resin layer 6 fills the opening 5X of the conductor layer 5 and is formed thicker than the total thickness of the conductor layer 5 and the adhesive layer 4. Further, it can be formed on the conductor layer 5 in the non-opening portion 5Y of the conductor layer 5. At this time, the thickness of the transparent resin layer 6 is determined in consideration of the thickness of the conductor layer 5 and the thickness of the adhesive layer 4 so that the surface of the transparent resin layer 6 becomes flat. It is preferable that the opening 5X and the non-opening 5Y are different from each other.

  In the electromagnetic wave shielding filter 1 according to the present invention shown in FIG. 1, other constituent materials can be formed as necessary. FIG. 2 shows a substrate 7 formed on the surface of the transparent resin layer 6 of the electromagnetic wave shielding filter 1 of FIG.

  Hereinafter, the electromagnetic wave shielding filter of the present invention will be described in order from the transparent substrate 2 for each layer.

(Transparent substrate)
As the transparent base material 2, any material can be used as long as it satisfies the requirements necessary for the base material of the electromagnetic wave shielding filter. For example, light transmittance, mechanical strength, heat resistance, insulation, etc. In consideration of the above, it is possible to appropriately select and use one according to the application. For example, various resin materials and inorganic materials such as glass can be used.

  Specific examples of the resin material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene resin, polypropylene resin, polystyrene resin, ethylene vinyl acetate copolymer resin (EVA), and cyclic polyolefin. Resin, norbornene resin, triacetyl cellulose resin, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polysulfone resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, acrylic resin, urethane acrylate resin, acrylate resin , Methacrylate resins, silicone resins containing polyorganosilsesquioxane, urethane resins, epoxy resins, and the like. Of these, a polyethylene terephthalate film is most suitable in terms of transparency, heat resistance, ease of handling, and cost. From the viewpoint of durability, polyethylene naphthalate film, polyimide film, cyclic polyolefin resin film, norbornene resin film, epoxy (meth) acrylate resin film, urethane (meth) acrylate resin film, (meth) acrylate resin film, poly An organosilsesquioxane-containing silicone resin film is preferred.

  In addition, additives such as an ultraviolet absorber, a filler, a plasticizer, and an antistatic agent can be appropriately added to these resins as necessary.

  Examples of the glass include quartz glass, borosilicate glass, and soda lime glass. More preferably, the glass has a low coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and contains no alkali components in the glass. Glass etc. are mentioned, It can also serve as the electrode substrate used as the front substrate etc. of a display.

  In the present invention, the total visible light transmittance is particularly preferably 70% or more. The transparent substrate does not necessarily need to be colorless and transparent, may be colored to such an extent that the object of the present invention is not hindered, and can be used as a single layer, but a multilayer film in which two or more layers are combined It may be used as

  The thickness of the transparent substrate can be determined according to the application. In the case of a transparent substrate made of a transparent resin, the thickness is 5 to 500 μm, preferably 10 to 100 μm, more preferably 25 to 50 μm. On the other hand, when the transparent substrate is glass, a thickness of about 0.4 mm to 5 mm is usually preferable. In any material, if the thickness is less than the above, the mechanical strength is insufficient, causing warping, sagging, breakage, etc. If the thickness exceeds the above, it becomes excessive performance and high cost, and thinning is difficult. .

  As the transparent substrate, a sheet (or film) or plate made of these inorganic materials, organic materials, or the like can be applied, and the transparent substrate is a part of a display main body made up of a front substrate, a back substrate, and the like. Although it may be combined with the front substrate which is a component, in the form using an electromagnetic wave shielding filter as a front filter disposed in front of the front substrate, the sheet is superior to the plate in terms of thinness and lightness, Needless to say, the resin sheet is superior to the glass plate in that it does not break. In addition, the transparent substrate should be handled in the form of a continuous belt-like sheet at least at the initial stage of production, such as formation of a conductor layer, in that the electromagnetic shielding filter can be continuously produced to improve productivity. Is preferred.

  In the case of a transparent substrate made of a resin material, the surface thereof is appropriately subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, etc. It can be performed.

[Conductor layer]
The conductor layer 5 is indispensable for the electromagnetic wave shielding filter according to the present invention, and serves as the electromagnetic wave shielding function of the filter according to the present invention, and has an opening so that the conductive layer is made of a light-impermeable material. In this case, sufficient light transmittance is exhibited.

  The conductor layer is not particularly limited as long as it is a substance having sufficient conductivity to exhibit an electromagnetic wave shielding function. Usually, a metal layer is preferable in terms of good conductivity. As the conductor layer, an alloy in which one kind or a combination of two or more kinds of metals such as copper, aluminum, nickel, iron, gold, silver, stainless steel, tungsten, chromium, and titanium can be used. Copper, aluminum or nickel is suitable in terms of conductivity, ease of circuit processing, and cost, and a metal foil having a thickness of 3 to 40 μm is preferable. This is because if the thickness exceeds 40 μm, it is difficult to form the line width and the viewing angle becomes narrow, and if the thickness is less than 3 μm, the surface resistance increases and the shielding effect is poor.

  It is preferable that the conductive material is copper and at least the surface of the conductive material is blackened because of high contrast. Further, the conductive material can be prevented from being oxidized and faded over time. The blackening treatment may be performed before and after the formation of the opening, but can be performed using a method performed in the printed wiring board field after the normal formation. As a preferable method, for example, a method of treating in an aqueous solution of sodium chlorite, sodium hydroxide, trisodium phosphate or the like can be mentioned. The aqueous solution used here is particularly preferably a sodium chlorite concentration of 31 g / l, a sodium hydroxide concentration of 15 g / l, and a trisodium phosphate concentration of 12 g / l, and the treatment conditions are 95 ° C. for 2 minutes. Is most preferred.

  It is preferable that the conductive material is a paramagnetic metal because it has excellent magnetic field shielding properties.

  If it is necessary to reduce the thickness of the conductor layer, one or more of thin film formation techniques such as vacuum deposition, sputtering, ion plate, chemical vapor deposition, electroless / electroplating, etc. This can be achieved by combining these methods. Although the film thickness of the conductive material can be 40 μm or less, the thinner the display, the wider the viewing angle of the display, which is preferable as the EMI shielding material, and more preferably 18 μm or less.

  The opening of the conductor layer can be any geometric figure, for example, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square such as a square, a rectangle, a rhombus, a parallelogram, a trapezoid, a (positive) hexagon, ( (Positive) Octagon, (Positive) Dodecagon, (Positive) N-gonal such as Dodecagon, Circle, Ellipse, Star, etc. It can also be used in combinations of more than types. From the viewpoint of EMI shielding properties, the triangle is the most effective, but from the viewpoint of visible light transmittance, if the same line width is used, the larger the n number of the (positive) n-gon, the higher the aperture ratio and the greater the visible light transmittance. It is.

  As a method of drawing such a geometric figure, it is effective from the viewpoint of workability to produce the transparent substrate with the conductive material by a chemical etching process. In addition, there is a method in which a photosensitive resin layer disposed on a transparent plastic substrate is exposed and developed using a mask on which a geometric figure is drawn, and a geometric figure is formed by combining electroless plating or electroplating.

  Such a geometric figure preferably has a line width of 40 μm or less, a line interval of 200 μm or more, and a line thickness of 40 μm or less. Further, the line width is preferably 25 μm or less from the viewpoint of non-visibility of the geometric figure, and the line interval is more preferably 500 μm or more and the line thickness is 18 μm or less from the viewpoint of visible light transmittance. Visible light transmittance improves as the line spacing increases, but if this value becomes too large, the EMI shielding properties deteriorate, so it is preferable to set it to 1 mm or less. When the line interval becomes complicated due to a combination of geometric figures or the like, the area is converted into a square area based on the repetition unit, and the length of one side is set as the line interval.

[Adhesive layer]
The adhesive layer 4 is for bonding and fixing the conductor layer 5. In the electromagnetic wave shielding filter according to the present invention, since the adhesive layer 4 is not formed in the opening of the conductor layer, the adhesive layer 4 does not lower the transparency of the electromagnetic wave shielding filter. In the present invention, since the adhesive layer can be formed with an arbitrary adhesive without considering transparency, it is possible to obtain a high adhesive strength that is difficult to realize with a conventional transparent adhesive.

  The adhesive that forms the adhesive layer 4 is not particularly limited, and a known adhesive can be appropriately employed. For example, urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives and the like can be mentioned. Among them, urethane adhesives are preferable in terms of adhesive strength and the like. Such urethane adhesives include two-component curable urethane resin adhesives, and two-component curable urethane resin adhesives include various hydroxyl groups such as polyether polyol, polyester polyol, and acrylic polyol. Examples thereof include an adhesive using a two-component curable urethane resin containing a group-containing compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

  The specific formation method of an adhesive bond layer is not specifically limited, A well-known method is employ | adopted suitably. Examples thereof include coating methods such as roll coating, comma coating, and gravure coating, and printing methods such as screen printing and gravure printing. The thickness of the adhesive layer (at the time of drying) is not particularly limited, but is usually 1 to 20 μm in the non-opening portion of the conductor layer 5, but is more preferable in terms of adhesive strength, cost, workability, and the like. Is 1-10 μm.

  In the present invention, as described above, the adhesive layer is not a part of the entire surface of the stopper layer on the transparent substrate, but a part that is in contact with the conductive material in order to improve optical characteristics, that is, light transmittance. Only form. As a method for this, a method of removing the adhesive layer not covered with the conductive material is conceivable, but a method of previously providing a stopper layer for stopping the removal at a predetermined position and performing the removing step is preferable. With this configuration, when assembled as an image display unit, that is, a display panel, the light transmittance of the display unit is increased, and as a result, a bright and clear display is possible. In addition, useless coating portions of the adhesive material are eliminated, and the material cost can be reduced and the filter parts can be reduced in weight.

  As a method for realizing such a form, (1) a method in which an adhesive is applied to a conductive material in which a geometrical figure is chemically etched and bonded to a transparent substrate, and (2) an adhesive is applied to a transparent substrate. A method of forming a geometric figure on the conductive material by chemical etching and then removing the adhesive layer from the conductive material surface side after applying and bonding with the conductive material. In any of the methods, since the adhesive layer may protrude from the geometric figure forming portion, an effective effect can be obtained in the adhesive layer removing step.

[Adhesive layer removal treatment]
The adhesive layer removal treatment can be performed by a method of removing the adhesive layer by the following method using the conductive material having the opening as a mask. (1) Plasma etching method, (2) Reactive plasma etching method, (3) Reactive etching method, (4) Photoetching method, (5) Polishing method, (6) Sand blast treatment, (7) Dry ice blast treatment , (8) high pressure fluid removal method, (9) flame treatment, (10) corona treatment, (11) removal method by ozone treatment, and (12) photolithography method can be used.

  (1) As a specific method of the plasma etching method, a conductive material such as argon, helium, and hydrogen is not etched under reduced pressure, atmospheric pressure or increased pressure, and only the adhesive can be removed. One type of gas or a mixture of two or more types of gas is introduced, and discharge is formed by methods such as plasma discharge, glow discharge, arc discharge, magnetron discharge, microwave discharge, surface wave plasma discharge, corona discharge, and adhesive. It is a method of removing. Any processing pressure can be appropriately selected as long as the apparatus is configured to quickly remove the decomposed and etched adhesive from the processing layer. Further, as the plasma discharge format, any discharge format can be appropriately used according to the processing pressure.

When performing the reactive plasma etching method (2), at least one kind of reactive gas, preferably oxygen, nitrogen, carbon dioxide, ammonia, NF ₃ , CF ₄ , SF ₆ is introduced into the processing gas, Plasma discharge, glow discharge, arc discharge, magnetron discharge, microwave discharge, surface wave plasma discharge, corona discharge, etc. are used to form the discharge, which is not only removed by physical action, but also uses chemical reactivity. To do. This method has the advantage of improving the processing speed. Further, the gases used for plasma plasma etching such as argon, helium and hydrogen may be mixed and used at the same time.

  As a method of performing the (3) reactive etching, a hot wire method can be used under reduced pressure. More specifically, a refractory metal such as tungsten is formed in a wire shape or mesh shape, electric power is applied to the metal wire or mesh, and the metal wire or mesh is heated at a high temperature. At this time, the gas supplied for the etching process is decomposed into ions, electrons, radicals, etc. by the heat energy, light energy, and electron beam energy generated from the metal wire or mesh, and etching occurs on the substrate surface. Is possible. As the etching process gas, nitrogen, ammonia, hydrogen, helium, argon, or the like can be used by mixing at least one kind or a mixture of two or more kinds.

Similarly, in (4) photoetching, CO ₂ laser, Ar laser, He—Ne laser, excimer laser, etc. are used to introduce and excite etching gas to form these active reactive species such as ions, electrons, radicals, etc. Thus, the adhesive layer on the substrate surface can be removed.

  The methods described in (1) to (4) are classified as dry etching methods, but such dry etching methods require the use of special chemicals or abrasives to remove the adhesive. In addition, since no residue remains on the surface of the substrate, the substrate can be processed cleanly, which is a preferable method for the removal method of the present invention.

  (5) The polishing method is a method of removing the adhesive by supplying an abrasive to the surface of the substrate and polishing the surface of the substrate.

  (6) In the sand blasting method, it is possible to remove the adhesive by a rotating operation on the surface of the substrate, or remove the fine particles by colliding with the surface of the substrate at a high pressure. After using these methods, a cleaning step using pure water or a chemical solution may be used. These methods are suitable as removal methods because the optimum processing conditions can be easily optimized by adjusting the type of abrasive and the applied pressure.

  (7) The dry ice blasting method uses solid dry ice as a blasting material, and removes the adhesive by colliding 0.1 to 10 mm size dry ice on a substrate with a pressure source such as a compressor at a high pressure. is there. In the dry ice blast method, a pressure of 1 to 10 MPa is applied in the case of the high pressure type, 0.1 to 1 MPa in the standard type, and 0.01 to 0.1 MPa in the low pressure type. In addition, this method also includes a powder shot method in which liquefied carbon dioxide gas is used as a dry ice source and is supplied in fine particles by nitrogen pressurization when necessary to suppress damage to the substrate. Any of these methods is preferable in that dry ice or carbon dioxide gas is vaporized and does not remain on the substrate after collision with the substrate.

  (8) The high pressure fluid removal method is a method in which a high pressure of 1 MPa or more is applied to a liquid such as pure water, a chemical solution, or a cleaning solution, and high pressure treatment is performed on the surface of the substrate. The supply pressure of the liquid is preferably 1 MPa or more, more preferably 5 MPa or more, and further preferably 10 MPa or more. The high-pressure liquid may be supplied continuously or intermittently. When performing this treatment on a roll-shaped substrate, the substrate can be stably held against high-pressure impacts such as a drum or roller, and is supported and removed by a mechanism that can sufficiently apply high pressure. In order to efficiently remove an object, the incident angle of the high-pressure liquid to the substrate is preferably 0 to 90 degrees. In order to further enhance the removal effect, the liquid temperature may be adjusted to a high temperature in the range of 40 ° C to 80 ° C. In addition, as chemicals and cleaning liquids, alcohols such as sodium hydroxide, potassium hydroxide, methanol, ethanol and isopropyl alcohol (IPA), organic substances such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), ethyl acetate, toluene and cyclohexanone are used. A solvent can be used. Further, a plurality of pure water, chemical solution and cleaning solution may be used by mixing, a plurality of same or different processes may be repeatedly performed, and a rinsing process or a substrate drying process may be included in the final process. This method is a preferable method because not only the adhesive can be efficiently removed, but also damage to the substrate is small, and impurities other than pure water and chemicals are not mixed.

  (9) The flame treatment is a method of decomposing and removing the adhesive by a flame, and a removal step using a liquid such as pure water or a chemical solution may be performed as necessary. This method has an advantage that the apparatus cost is low.

  (10) The corona treatment is a method in which corona discharge is formed in the atmosphere and the adhesive is decomposed and removed, and a cleaning process using pure water or a chemical solution may be used after corona discharge. This method has an advantage that the apparatus cost is low.

  (11) Ozone treatment is a method of generating ozone by an ozone generator and supplying it to the surface of a substrate to decompose and remove the adhesive. After the ozone treatment, a removal step using pure water or a chemical solution may be performed as necessary. This method has an advantage that it is highly decomposable and can be processed at high speed.

  (12) As a photolithography method, it is possible to use a method in which an adhesive contains a functional group that is sensitive to ultraviolet rays or electron beams. At this time, a positive photosensitive material is used for the removal portion, and the metal foil can be used as a light shielding mask, so that only the exposed portion can be efficiently removed.

[Stopper layer]
Next, the stopper layer 3 will be described. As shown in FIG. 1, the stopper layer 3 is formed so as to cover the surface of the transparent substrate 2 at an intermediate position between the transparent substrate 2 and the adhesive layer 4. Since this stopper layer 3 has high resistance to the adhesive layer removal treatment, the influence of the adhesive layer removal treatment is prevented from extending beyond the stopper layer 3 to the surface of the transparent substrate 2 that is the lower layer. The Therefore, it is effectively prevented that the transparent base material layer is eroded by the adhesive layer removing process, and the characteristics of the transparent base material layer, particularly the surface characteristics and the optical characteristics are changed by the adhesive layer removing process.

  Thereby, it is prevented that the mechanical properties and optical properties, in particular, light transmittance, of the transparent substrate and the electromagnetic wave shielding filter according to the present invention are deteriorated by the adhesive layer removal treatment. And when this stopper layer 3 is formed, since it is not necessary to determine the processing conditions of the adhesive layer removing process in consideration of the characteristic deterioration of the transparent substrate, etc., when the stopper layer is not formed In comparison, the optimum conditions and allowable range for the adhesive layer removal process are expanded. Therefore, the removal process of the adhesive layer can be performed more efficiently, uniformly and reliably.

  The stopper layer preferably has a removal rate of 1/2 or less, preferably 1/10 or less, more preferably 1/20 or less of the adhesive layer. If such a removal rate is obtained, it can function effectively as a stopper layer. Here, the removal speed of the stopper layer is 1/2 or less of the adhesive layer, specifically, when the stopper layer and the adhesive layer are subjected to the adhesive layer removal treatment under the same conditions, It means that the removal rate of the stopper layer is 1/2 or less of the removal rate of the adhesive layer. Note that the evaluation of the reduction rate of the stopper layer and the adhesive layer is obtained by reducing the film thickness per unit time under each removal treatment condition, typically under the treatment conditions shown in the examples.

  Furthermore, the stopper layer is transparent because it is used in the opening of the conductor layer, which is a light transmitting portion, and preferably has an average transmittance of 70% or more in the visible light region. In order to have such a removal rate ratio and transparency, the stopper layer is any one of an inorganic oxide film, an inorganic nitride film, an inorganic carbon film, an inorganic oxynitride film, an inorganic oxycarbide film, and an inorganic oxynitride carbon film. The inorganic element is preferably a film containing one or more of silicon, aluminum, chromium, magnesium, calcium, titanium, niobium, molybdenum, tantalum, indium, tin, and zirconium. These materials have sufficient removal resistance and light transmittance in the visible light region, and have an advantage that the manufacturing method is simple, and thus are suitable as a stopper layer.

  In the production of the electromagnetic wave shielding filter according to the present invention, the method for forming the stopper layer is preferably an evaporation method, a sputtering method, an ion plating method, an ion plating method using a pressure gradient plasma gun, a plasma CVD method, It can be performed by a vacuum film forming method such as a hot wire CVD method, an atmospheric pressure plasma CVD method, or a surface wave plasma CVD method. Among these, the plasma CVD method or the pressure gradient ion plating method is more preferable. Each of these methods is referred to herein as a dry method.

  The stopper layer 3 can be formed not only by the vacuum film forming method described above but also by a sol-gel method, a spray pyrolysis method, or a chemical solution liquid layer method. Each of these methods is referred to herein as a wet method.

  A preferable sol-gel method of the present invention includes a method of applying an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides and / or hydrolysates thereof, and then drying by heating. it can. As the water-soluble polymer, for example, polyvinyl alcohol can be used, and as the metal alkoxide, for example, tetraethoxysilane, triisopropoxyaluminum, titanium tetraisopropoxide, or a mixture thereof can be used.

The spray pyrolysis method is a method for obtaining a metal oxide film by spraying a solution containing the metal salt constituting the metal oxide film onto a high-temperature substrate, and evaporating the solvent to be supplied by heating the substrate. In this method, the metal oxide film is obtained by evaporation and thermal decomposition reaction of the metal source. Specifically, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-145615, a raw material solution is prepared by adding hydrogen peroxide or aluminum acetylacetonate to a solution containing a TiO ₂ precursor, and the substrate is kept at a high temperature. A method of thermally decomposing the TiO ₂ precursor into TiO ₂ by intermittently spraying the raw material solution to obtain a TiO ₂ thin film on the substrate can be used.

In addition, the chemical solution liquid layer method is based on contacting a metal oxide film forming solution in which a metal salt or metal complex is dissolved as a metal source with a substrate heated to a temperature equal to or higher than the metal oxide film forming temperature. This is a method for obtaining a metal oxide film on a material. The metal oxide forming solution may contain at least one of an oxidizing agent and a reducing agent, ceramic fine particles, an auxiliary ion source, a surfactant, and the like as additives. Specifically, when forming a cerium oxide film (CeO ₂ ), cerium nitrate (Ce (NO ₃ ) ₃ ) as a metal source, borane-dimethylamine complex (also known as dimethylamine borane, DMAB) as a reducing agent, and solvent In this method, water is prepared and supplied onto a substrate heated to a temperature of about 150 to 600 ° C. or higher by spraying, dipping, roll coating, or the like to form a film.

  The thickness of the stopper layer is preferably 5 nm to 100 μm. The optimum region of this film thickness varies depending on the forming method. That is, when the stopper layer is formed by a dry method, the optimum film thickness is 5 nm to 1000 nm, preferably 5 nm to 300 nm, and more preferably 5 nm to 100 nm. If it is less than 5 nm, the entire surface of the substrate cannot be covered with the stopper layer, and a sufficient stopper effect cannot be obtained. On the other hand, if it exceeds 1000 nm, productivity and cracking are not preferable. When the stopper layer is formed by a wet method, the optimum film thickness is 500 nm to 100 μm, preferably 1 μm to 50 μm, more preferably 1 μm to 30 μm. As described above, the minimum required film thickness may be 5 nm or more. However, in the case of a wet process, it is difficult to form a uniform film with a thickness of less than 0.5 μm. Moreover, when it exceeds 100 micrometers, it is unpreferable from the surface of productivity. In the present invention, a plurality of forming methods may be used in combination as necessary.

  The formed stopper layer preferably has a surface average roughness Ra of 50 nm or less or a maximum surface height difference PV of 500 nm or less. Thus, when the surface is uniform, a stopper effect can be obtained uniformly and reliably when the adhesive layer is removed. Moreover, a highly transparent film can be obtained without causing optical scattering.

  Moreover, it is preferable that the refractive index difference of a stopper layer and a transparent base material shall be 0.15 or less. Thus, a highly transparent film can be obtained because the difference in refractive index between the transparent substrate and the stopper layer is small.

On the other hand, the refractive index difference between the stopper layer and the transparent substrate may be 0.15 or more. In this case, it is possible to obtain an antireflection effect using optical reflection. In this case, a low refractive index layer or a high refractive index layer may be formed as a single layer with respect to the substrate, or a three-layer structure (low refractive index layer / high refractive index layer / medium refractive index layer), four layers. Any conventionally known layer configuration such as configuration (low refractive index layer / high refractive index layer / low refractive index layer / high refractive index layer) can be applied. As the low refractive index layer, for example, SiO ₂ can be appropriately used TiO ₂ , NbO ₂ , Si ₃ N ₄ as the high refractive index material, and ITO or the like as the middle refractive index layer.

[Transparent resin layer]
The transparent resin for forming the transparent resin layer 6 is not particularly limited as long as it is a transparent resin. When the resin is in contact with the conductor layer 5 or in contact with both the conductor layer 5 and the stopper layer 3, the stopper layer is used. A known resin can be appropriately employed in consideration of the adhesiveness with the resin.

  When the transparent resin layer 6 has adhesiveness, the electromagnetic wave shielding filter according to the present invention is directly attached to a display such as a CRT, PDP, liquid crystal, EL or the like by using the adhesiveness. Or can be attached to a plate or sheet such as an acrylic plate or a glass plate and used for a display.

  Transparent resin types include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrahydroxyphenylmethane type epoxy resin, novolac type epoxy resin, resorcin type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin Epoxy resins such as alicyclic and halogenated bisphenol can be used. These express suitable visible light transmittance.

  Other than epoxy resins, natural rubber, polyisoprene, poly 1,2-butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-2-tert-butyl-1,3-butadiene, poly-1 (Di) enes such as 1,3-butadiene, polyethers such as polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether and polyvinyl butyl ether, polyesters such as polyvinyl acetate and polyvinyl propionate, polyurethane, Examples thereof include ethyl cellulose, polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, polysulfide, and phenoxy resin.

  In addition to the above resins, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, poly-t-butyl acrylate, poly-3-ethoxypropyl acrylate, polyoxycarbonyl tetramethacrylate, polymethyl acrylate), poly Isopropyl methacrylate, polydodecyl methacrylate, polytetradecyl methacrylate, poly-n-propyl methacrylate, poly-3,3,5-trimethylcyclohexyl methacrylate, polyethyl methacrylate, poly-2-nitro-2-methylpropyl methacrylate, polytetracarba Poly (meth) acrylic acid esters such as nyl methacrylate, poly-1,1-diethylpropyl methacrylate and polymethyl methacrylate can be used. That. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used.

  Moreover, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, etc. can also be used as a copolymer resin of acrylic resin and other than acrylic. In particular, epoxy acrylate and polyether acrylate are excellent from the viewpoint of adhesiveness. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether (Meth) acrylic acid adducts such as adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether Is mentioned. Epoxy acrylate has a hydroxyl group in the molecule and is effective in improving adhesiveness, and these copolymer resins can be used in combination of two or more as required. The polymer used as the main component of the adhesive has a weight average molecular weight of 1,000 or more. When the molecular weight is less than 1,000, the cohesive force of the composition is too low, so that the adhesion to the adherend is lowered.

  Curing agents include amines such as triethylenetetramine, xylenediamine, and diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride, and diaminodiphenyl sulfone. , Tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polymer. If the amount added is less than 0.1 parts by weight, curing may be insufficient, and if it exceeds 50 parts by weight, excessive crosslinking may occur, which may adversely affect adhesiveness. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the transparent resin layer used by this invention as needed. Then, the resin composition of this adhesive is applied to cover a part or the whole surface of the base material of the constituent material provided with a geometric figure drawn with a conductive material on the surface of the transparent plastic base material, After the solvent drying and heat curing steps, the transparent resin layer in the present invention can be obtained.

  When the transparent resin layer obtained above has adhesiveness, it can be directly attached to a display such as a CRT, PDP, liquid crystal, EL or the like, or another substrate 7 such as an acrylic plate or glass. It can be attached to a plate or sheet such as a plate and used for a display.

<Example of production of electromagnetic wave shielding filter 1>
A transparent PET film with a thickness of 50 μm is used as a roll-shaped transparent plastic substrate having a width of 600 mm, and a layer serving as an adhesive removal stopper layer is formed thereon by forming a SiO _X film by a stopper layer 1 (PECVD method) described later) did. Next, the roughened surface of the electrolytic copper foil having a thickness of 18 μm, which is a conductive material, is epoxy with an epoxy adhesive sheet (Nikaflex SAF; manufactured by Nikkan Kogyo Co., Ltd.) serving as an adhesive layer thereon. The laminate was heated and laminated under the conditions of 180 ° C. and 30 kgf / cm ² so as to be on the system adhesive sheet side.

  The resulting PET film with copper foil is subjected to a photolithographic process (resist film pasting-exposure-development-chemical etching-resist film peeling), and a geometric pattern of a copper lattice pattern having a line width of 25 μm and a line interval of 500 μm is formed on the PET film. Forming material 1 was obtained.

  This constituent material 1 is subjected to the adhesive removal method 1 (reactive plasma etching process) described later, and the adhesive layer not covered with the electrolytic copper foil has a cross-sectional shape at the center in the substrate width direction as shown in FIG. It was removed to be just etch. Under the present circumstances, the cross-sectional shape in a 100-mm position was measured from the base-material width direction edge part, and it was evaluated which cross-sectional shape of FIGS. 3-7 has. An electromagnetic wave shielding filter 1 according to the present invention having electromagnetic shielding properties and transparency by applying and drying a transparent resin composition to be described later on the reactive plasma etching-treated constituent material 1 so as to have a dry coating thickness of about 40 μm. Got.

Then, the electromagnetic wave shielding filter 1 according to the invention commercial acrylic plate using a roll laminator (Komogurasu; manufactured by Kuraray Co., Ltd., thickness 3 mm) 110 ° C., the heated crimped under the conditions of 20 kgf / cm ^2.

<Example of production of electromagnetic wave shielding filter 2>
A transparent PET film having a thickness of 25 μm is used as a roll-shaped transparent plastic substrate having a width of 600 mm, and a layer serving as an adhesive removal stopper layer is formed thereon by a stopper layer 2 (SiO _X film formation by an ion plating method) described later. Formed. On top of this, an aluminum foil having a thickness of 25 μm, which is a conductive material, is placed at 170 ° C. and 20 kg / cm by a roll laminator through Pyrarax LF-0200 (manufactured by DuPont Japan Limited, acrylic adhesive film) serving as an adhesive layer. Lamination was performed under the conditions of ² . This aluminum PET film was subjected to the same photolithography process as in the production example of the electromagnetic wave shielding filter 1, and a geometric figure of an aluminum lattice pattern having a line width of 25 μm and a line interval of 250 μm was formed on the PET film to obtain a constituent material 2. .

  This constituent material 2 was subjected to the adhesive layer removing method 1 (reactive plasma etching process) described later, and the adhesive layer not covered with the aluminum foil was removed. The substrate was removed so that the cross-sectional shape at the center in the width direction of the substrate was just etched as shown in FIG. Under the present circumstances, the cross-sectional shape in a 100-mm position was measured from the base-material width direction edge part, and it was evaluated which cross-sectional shape of FIGS. 3-7 has. An electromagnetic wave shielding filter according to the present invention having an electromagnetic wave shielding property and transparency by applying and drying a transparent resin composition, which will be described later, on this reactive plasma-etched constituent material 2 so that the dry coating thickness is about 30 μm. 2 was obtained.

And the electromagnetic wave shield filter 2 by this invention was heat-pressed on the commercially available acrylic board using the hot press machine at 110 degreeC, 30 kgf / cm < ² >, and the conditions for 30 minutes.

<Transparent resin composition 1>
100 parts by weight of TBA-HME (manufactured by Hitachi Chemical Co., Ltd .; high molecular weight epoxy resin, Mw = 300,000), 25 parts by weight of YD-8125 (manufactured by Toto Kasei Co., Ltd .; bisphenol A type epoxy resin), IPDI (Hitachi) Chemical Industry Co., Ltd .; mask isocyanate) 12.5 parts by weight, 2-ethyl-4-methylimidazole 0.3 parts by weight, methyl ethyl ketone (MEK) 330 parts by weight, cyclohexanone 15 parts by weight, and the components of the adhesive, A varnish of the transparent resin composition 1 was prepared by dissolving in MEK and cyclohexanone.

<Transparent resin composition 2>
YP-30 (manufactured by Toto Kasei Co., Ltd .; phenoxy resin, Mw = 60,000) 100 parts by weight, YD-8125 (manufactured by Toto Kasei Co., Ltd .; bisphenol A type epoxy resin), 10 parts by weight, IPDI (Hitachi Chemical Industries, Ltd.) Co., Ltd .; mask isocyanate) 5 parts by weight, 0.3 parts by weight of 2-ethyl-4-methylimidazole, 285 parts by weight of MEK, 5 parts by weight of cyclohexanone, and components of the above adhesive were dissolved in MEK and cyclohexanone. A varnish of the transparent resin composition 2 was prepared.

<Transparent resin composition 3>
YP-30 (manufactured by Toto Kasei Co., Ltd .; phenoxy resin, Mw = 60,000) 100 parts by weight, YD-8125 (manufactured by Toto Kasei Co., Ltd .; bisphenol A type epoxy resin), 10 parts by weight, IPDI (Hitachi Chemical Industries, Ltd.) Co., Ltd .; mask isocyanate) 5 parts by weight, 0.3 parts by weight of 2-ethyl-4-methylimidazole, 285 parts by weight of MEK, 5 parts by weight of cyclohexanone, and components of the above adhesive were dissolved in MEK and cyclohexanone. A varnish of the transparent resin composition 3 was prepared.

<Adhesive layer removal treatment method 1 (reactive plasma etching)>
A take-up plasma processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as a plasma processing surface. Using an evacuation pump, the inside of the apparatus is depressurized to 1 × 10 ⁻³ Pa, and then oxygen and argon are introduced as reactive plasma process gases at 1 slm and 300 sccm, respectively, and the substrate is transported. The exhaust system was adjusted so that the pressure was a constant pressure of 30 Pa. Using a power source having a frequency of 40 kHz between the electrodes, a plasma discharge was formed at an input power of 2 kW to perform reactive plasma etching. At this time, the substrate conveyance speed was adjusted so that the etching was completed when the adhesive layer was completely removed.

<Adhesive Layer Removal Treatment Method 2: Plasma Etching (1)>
A take-up plasma processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as a plasma processing surface. Using an evacuation pump, the inside of the apparatus is depressurized to 1 × 10 ⁻³ Pa, and then, as a reactive plasma processing gas, argon is introduced at 1 slm and 300 sccm, and conveyance of the substrate is started, and the pressure in the processing chamber is set to 30 Pa. The exhaust system was adjusted to a constant pressure. Using a power source having a frequency of 40 kHz between the electrodes, a plasma discharge was formed at an input power of 2 kW to perform reactive plasma etching. At this time, the substrate conveyance speed was adjusted so that the etching was completed when the adhesive layer was completely removed.

<Adhesive layer removal treatment 3: high pressure fluid removal method>
A take-up removal device having a substrate transport mechanism and a processing chamber capable of continuous processing on a long roll substrate was prepared, and the metal surface side of the substrate was set as a processing surface. The processing unit is supplied with pure water in the form of a spray at a high pressure of 12 MPa with an incident angle of 30 degrees on the surface of the base material continuously supplied onto the drum. The adhesive layer was removed. The pure water was supplied at a temperature adjusted to 40 ° C. Moreover, after the removal process, the rinse process and the drying process were performed, and it wound up in roll shape again.

<Adhesive layer removal treatment method 4: atmospheric pressure plasma etching>
A take-up plasma processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as a plasma processing surface. Using an evacuation pump, the inside of the apparatus is depressurized to 1 × 10 ⁻³ Pa, and then, as a plasma etching gas, argon is introduced at 1 slm and helium at 300 sccm, and the substrate is transferred, and the pressure in the processing chamber is set to 1 atm The exhaust system was adjusted so that An electric power of 0.5 kW was applied between the electrodes, a plasma discharge was formed, and atmospheric pressure plasma etching was performed. At this time, the substrate conveyance speed was adjusted so that the etching was completed when the adhesive layer was completely removed.

<Adhesive layer removal treatment method 5: reactive etching>
A take-up plasma processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as a processing surface. In the processing chamber, a hot wire source using a tungsten wire was installed between the base material and the gas supply port at a position 50 mm on average from the base material. The substrate was sequentially conveyed by a substrate conveyance mechanism, and the substrate was processed on a drum whose temperature was adjusted to 0 ° C. Using an evacuation pump, the inside of the apparatus is depressurized to 1 × 10 ⁻³ Pa, and then ammonia and hydrogen are introduced as reactive plasma processing gases by 500 sccm and 300 sccm, respectively, and the conveyance of the substrate is started. The exhaust system was adjusted to a constant pressure of 30 Pa. The tungsten wire was heated to 1500 ° C. by slidac, ammonia and hydrogen were activated, and the adhesive layer was removed by etching reaction on the substrate surface. In the film formation, the substrate conveyance speed was adjusted so that the etching was completed when the adhesive layer was completely removed.

<Adhesive layer removal treatment method 6: photoetching>
A winding type etching processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing with respect to a long roll base material was prepared, and the metal layer side of the base material was set as an etching processing surface. A CO ₂ laser was prepared as a photoetching light source in the processing chamber. The substrate processing apparatus sequentially moved to the transfer processing chamber, and the removal portion was irradiated with a CO ₂ laser to remove the adhesive layer.

<Adhesive layer removal treatment method 7: polishing method>
A roll-up type polishing processing apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as an etching processing surface. In the processing chamber, a drum for supporting the substrate was provided, and the abrasive was impacted by a shot blasting method on the substrate supplied onto the drum to physically remove the adhesive layer. After removing the adhesive layer, the substrate was wound up in a roll after washing and drying.

<Adhesion layer removal method 8: dry ice blasting method>
A take-up dry ice blasting apparatus having a base material transport mechanism and a processing chamber capable of continuous processing on a long roll base material was prepared, and the metal layer side of the base material was set as a blast processing surface. In the processing chamber, a drum for supporting the base material was provided, and the base material supplied on the drum was impacted by a shot blasting method using solid dry ice as a blast processing material to physically remove the adhesive layer.

<Adhesive layer removal treatment method 9: flame treatment method>
A take-up flame treatment apparatus having a substrate conveyance mechanism and a treatment chamber capable of continuous treatment with respect to a long roll substrate was prepared, and the metal layer side of the substrate was set as a flame treatment surface. The treatment chamber was provided with a drum that was temperature-controlled at 0 ° C. to support the substrate, and the substrate supplied on the drum was subjected to flame radiation treatment to remove the adhesive layer.

<Adhesive layer removal treatment method 10: corona treatment>
A take-up corona treatment apparatus having a substrate conveyance mechanism and a treatment chamber capable of continuous treatment on a long roll substrate was prepared, and the metal layer side of the substrate was set as a corona discharge treatment surface. In the processing chamber, a drum for supporting the substrate was provided, and the substrate supplied on the drum was subjected to corona discharge treatment to remove the adhesive layer.

<Adhesive layer removal treatment method 11: ozone treatment>
A take-up type ozone treatment apparatus having a substrate conveyance mechanism and a treatment chamber capable of continuous treatment with respect to a long roll substrate was prepared, and the metal layer side of the substrate was set as an ozone treatment surface. In the processing chamber, a drum for supporting the substrate was provided, and the substrate supplied on the drum was subjected to ozone treatment to remove the adhesive layer.

<Adhesive layer removal treatment method 12: photolithography method>
Prepare a take-up photolithographic processing device that has a substrate transport mechanism that can continuously process long roll substrates, an exposure chamber, a developing chamber, and a rinse chamber, with the metal layer side of the substrate as the processing surface I set it. The base material is transported sequentially by the base material transport mechanism, the exposure chamber is irradiated with ultraviolet rays with a high-pressure mercury lamp, then alkali development is performed in the development chamber, and finally, the substrate is rinsed with water in the rinse chamber, dried in the drying chamber, and then bonded. The layer was removed.

<Stopper Layer Fabrication Method 1: Silicon Oxide Film Formation by Plasma CVD Method>
A roll-like biaxially stretched polyester film (A4300, thickness 50 μm, width 600 mm, length 5000 m) prepared as a base film was prepared, and this was wound up by chemical vapor deposition shown in FIG. It was mounted in the chamber 102 of the apparatus 101. Next, the inside of the chamber of the chemical vapor deposition apparatus was depressurized to an ultimate vacuum of 4.0 × 10 ⁻³ Pa by an oil rotary pump and an oil diffusion pump.

  Further, tetraethoxysilane (TEOS) (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) and oxygen gas (manufactured by Taiyo Nippon Sanso Corporation, purity 99.9999% or more) were prepared as raw material gases.

  Next, one electrode plate 113 is disposed in the vicinity of the coating drum 105 so as to face the coating drum, and a high frequency voltage of 40 kHz is applied between the coating drum and the electrode plate (input power 2.5 kW). ). A gas inlet 109 is provided near the electrode plate in the chamber, TEOS is introduced at a flow rate of 0.2 slm, and oxygen gas is introduced at a flow rate of 4 slm, and the degree of opening and closing of the valve between the vacuum pump and the chamber is controlled. Thus, a thin film of silicon oxide was formed on the base film 2 while maintaining the pressure in the chamber during film formation at 6.7 Pa. The running speed of the base film was set to 8 m / min so that the thickness of the silicon oxide thin film was 500 mm. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

<Stopper Layer Fabrication Method 2: Silicon Oxide Film Formation by Ion Plating Method>
A roll-shaped biaxially stretched polyethylene terephthalate film (A4300, thickness 50 μm, width 600 mm, length 5000 m) prepared as a base film is provided with a return electrode as shown in FIG. The wound hollow cathode (pressure gradient) ion plating apparatus 201 was mounted in the chamber 202. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁴ Pa by an oil rotary pump and an oil diffusion pump.

  Moreover, silicon dioxide (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.97%, particle size 2 to 5 mm) was prepared as an evaporation source and placed on the anode 108.

Next, oxygen gas is introduced in the vicinity of the coating drum 204 of the chamber at a flow rate of 5 sccm, and the opening / closing degree of a valve between the vacuum pump and the chamber is controlled, so that the pressure in the chamber during film formation is 8 ×. The pressure was kept at 10 ⁻² Pa. Then, using a hollow cathode type plasma gun 207 into which argon gas has been introduced, the plasma flow is converged and irradiated to the evaporation source on the anode (hearth) to evaporate, and the evaporated molecules are ionized by the high-density plasma. A thin film of silicon oxide (SiOy (y = 1.5)) was formed on the material film. The running speed of the base film was set to 80 m / min so that the thickness of the silicon oxide thin film was 500 mm. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

<Stopper Layer Preparation Method 3: Silicon Oxynitride Film Formation by Sputtering Method>
A wound biaxially stretched polyethylene terephthalate film (Toyobo Co., Ltd. PET film A4300, thickness 50 μm, width 600 mm, length 1000 m) having a width of 60 cm was prepared as a base film, and the structure shown in FIG. It was mounted in a chamber 302 of a winding type dual cathode type sputtering apparatus 301. The sputtering apparatus 301 includes a vacuum chamber 302, a base film supply roll 303 a, a take-up roll 303 b, a coating drum 304, and partition plates 309 and 309 disposed in the vacuum chamber 302. Connected to the film forming chamber 305 through the film forming chamber 305, the target mounting table 306 disposed in the film forming chamber 305, the power source 307 for applying a voltage to the target, the plasma emission monitor 308, and the valve 311. The vacuum exhaust pump 310, a gas flow rate control device 312 for controlling the flow rate of nitrogen gas, and valves 313 and 314 for adjusting the supply amounts of oxygen gas and argon gas are provided.

  Next, silicon (single crystal, electric resistivity 0.02 Ωcm) was mounted on the target mounting table 306 in the film formation chamber 305 as a target material. The distance (TS distance) between this target and the substrate film was set to 10 cm. Next, oxygen gas (manufactured by Taiyo Nippon Sanso Corporation (purity: 99.9995% or more)), nitrogen gas (manufactured by Taiyo Nippon Sanso Corporation (purity: 99.9999% or more)) as an additive gas during film formation ) And argon gas (manufactured by Taiyo Nippon Sanso Corporation (purity 99.9999% or more)).

Next, the inside of the vacuum chamber 302 and the film formation chamber 305 was depressurized to a final vacuum degree of 2.0 × 10 ⁻³ Pa by a vacuum exhaust pump 310. Next, oxygen gas was introduced into the deposition chamber 305 at a flow rate of 0.5 sccm, and argon gas was introduced at a flow rate of 150 sccm. Nitrogen gas was simultaneously supplied. The nitrogen gas flow rate to be supplied was supplied at an optimum flow rate while controlling the Si emission intensity during plasma discharge to be constant using a plasma emission monitor (PEM-05, manufactured by Von Ardenne). Further, by controlling the degree of opening and closing of the valve 311 between the vacuum exhaust pump 310 and the film forming chamber 305, the pressure in the film forming chamber 305 is maintained at 0.1 Pa, and the base film is run, thereby performing a dual magnetron sputtering method. Thus, a stopper layer made of a silicon oxynitride film was formed on the base film with an input power of 3 kW. The substrate was run at 0.1 m / min so that the thickness of the formed thin film was 50 nm. The film thickness was determined by performing cross-sectional measurement using a scanning electron microscope (SEM; manufactured by Hitachi, Ltd., S-5000H).

<Stopper Layer Preparation Method 4: AlOx Film Formation by Vapor Deposition (PVD) Method>
A roll-shaped biaxially stretched polyethylene terephthalate film (A4300, thickness 50 μm, width 600 mm, length 5000 m) prepared as a base film is provided with an EB gun as shown in FIG. It was mounted in the vacuum chamber 402 of the take-up vapor deposition apparatus 401. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁴ Pa by an oil rotary pump and an oil diffusion pump.

  Also, aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.97%, block shape) was prepared as the evaporation source 404 and placed on the anode (hearth).

Next, oxygen gas is introduced at a flow rate of 1 slm in the vicinity of the coating drum 403 in the chamber, and the opening / closing degree of a valve between the vacuum pump and the chamber is controlled, so that the pressure in the chamber during film formation is 1 ×. The pressure was kept at 10 ⁻² Pa. Then, using an EB gun, the electron beam converges on the evaporation source on the crucible 410 with a power of 0.7 A × 35 kV, scans and irradiates and melts and evaporates to form an aluminum oxide thin film on the base film. Formed. The running speed of the base film was set to 80 m / min so that the thickness of the silicon oxide thin film was 500 mm. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

<Stopper Layer Fabrication Method 5; Formation of SiOx Film by Plasma CVD>
In the stopper layer manufacturing method 1, HMDSO (hexamethyldisiloxane, manufactured by Toray Dow Corning Silicone, SH200-0.65 cSt) and oxygen gas (Taiyo Nippon Sanso Corporation, purity 99.9999%) are used as the raw material gas instead of TEOS. ) Was prepared.

  During film formation, the HMDSO flow rate was 0.2 slm and oxygen gas was introduced 1 slm. The base film was run in exactly the same way as Preparation Method 1 except that the running speed of the silicon oxide carbide film was set to 10 m / min so that the thickness of the silicon oxide carbide film was 500 mm.

<Stopper Layer Fabrication Method 6; Silicon Nitride Carbide Film Formation by Plasma CVD Method>
In the stopper layer preparation method 1, HMDS (hexamethyldisilazane, manufactured by Shin-Etsu Chemical Co., Ltd.) and nitrogen gas (Taiyo Nippon Sanso Corporation, purity 99.9999%) were prepared as raw material gases instead of TEOS. During film formation, the HMDS flow rate was 0.2 slm and nitrogen gas was introduced at 1 slm. The base film was run in exactly the same way as Preparation Method 1 except that the running speed of the silicon oxide carbide film was set to 10 m / min so that the thickness of the silicon oxide carbide film was 500 mm.

<Stopper Layer Preparation Method 7; Formation of Silicon Oxynitride Carbide Film by Plasma CVD>
In the stopper layer preparation method 1, HMDS (hexamethyldisilazane, manufactured by Shin-Etsu Chemical Co., Ltd.), oxygen gas Taiyo Nippon Sanso Co., Ltd., purity 99.9999%), nitrogen gas (Taiyo Nippon Sanso) instead of TEOS as the raw material gas Co., Ltd., purity 99.9999%) was prepared. During film formation, the HMDS flow rate was 0.2 slm, oxygen gas 0.2 slm, and nitrogen gas 1 slm were introduced. The base film was run in exactly the same way as Preparation Method 1 except that the running speed of the silicon oxide carbide film was set to 10 m / min so that the thickness of the silicon oxide carbide film was 500 mm.

<Stopper Layer Preparation Method 8: Chromium Oxide Film Formation by Sputtering Method>
In the stopper layer manufacturing method 3, it was manufactured in exactly the same way as in manufacturing method 3, except that chromium was used instead of silicon as the target material.

<Stopper Layer Preparation Method 9: Magnesium Oxide Film Formation by Ion Plating Method>
In the stopper layer manufacturing method 2, a magnesium oxide film (MgO) was formed in exactly the same manner as in the manufacturing method 2, except that magnesium oxide was used instead of silicon dioxide as the evaporation source.

<Stopper Layer Preparation Methods 10-14: Oxide Film Formation by Sputtering Method>
The stopper layer manufacturing method 3 was manufactured in the same manner as the manufacturing method 3 except that each oxide film was formed using Ti, Nb, Ca, Mo, Ta) instead of silicon as a target material.

<Stopper Layer Preparation Method 15: ITO Film Formation by Ion Plating Method>
In the stopper layer preparation method 2, an ITO film was formed in exactly the same manner as in Preparation method 2, except that ITO was used instead of silicon dioxide as the evaporation source.

<Stopper Layer Preparation Method 16; Silicon Oxide Carbide Film Formation by Sol-Gel Method>
Materials having the following composition were prepared.
Water-soluble polymer: polyvinyl alcohol (polymerization degree 2400, saponification degree 98%)
Metal alkoxide: tetraalkoxysilane (TEOS)
-Diluting solvent: water / methanol mixed solvent-Hydrolysis catalyst: 0.1 mol / l HCl solution The above components are mixed so that the weight composition ratio is water-soluble polymer / metal alkoxide = 50:50 (parts by weight), A coating solution was obtained. A coating liquid A having the following composition was applied to the silicon oxide thin film layer with a thickness of 0.3 μm by a microgravure method, followed by drying in a drying oven at 180 ° C. to form an adhesive layer removal stopper layer.

<Stopper Layer Preparation Method 17; Titanium Oxide Film Formation by Spray Pyrolysis Method>
Dissolve titanium tetrachloride and titanium oxyacetylacetonate as titanium precursors in ethanol solvent, add hydrogen peroxide and aluminum acetylacetonate, dilute with alcohol, mix for 10 minutes with ultrasonic cleaner, A 2% by mass solution and a 3.0% by mass raw material solution were prepared. In a roll coater apparatus, the coating drum temperature was 150 ° C., nitrogen gas was used as a carrier gas, and spray coating was performed on the base material to produce a TiO ₂ thin film, which was used as an adhesive layer removal stopper layer.

<Stopper Layer Preparation Method 18; ZrOx Film Formation by Chemical Solution Liquid Layer Method>
Zirconium chloride (IV) (manufactured by Kanto Chemical Co., Inc.) 10 g of hydrogen peroxide solution was added to 1000 g of a 0.1 mol / l aqueous solution, and further a borane-dimethylamine complex (manufactured by Kanto Chemical Co., Ltd.) as a reducing agent was added at 1.0 mol / l. To obtain a metal oxide film forming solution.

  A roll-shaped biaxially stretched polyethylene terephthalate film (A4300, thickness 50 μm, width 600 mm, length 5000 m) is prepared as a base film, and this is a winding type equipped with a spray type coating mechanism. Attached to the coating apparatus. Next, the temperature of the coating unit drum is heated to 150 ° C., the metal oxide film forming solution is spray applied onto the base material, washed with water and dried, and then the base material on which the metal oxide film is formed is rolled. Winded up. The running speed of the base film was set so that the thickness of the silicon oxide thin film was 500 mm. Moreover, the film thickness of the formed thin film was calculated | required by performing a cross-sectional measurement using the scanning electron microscope (SEM; Hitachi Ltd. make, S-5000H).

Example 1
The transparent resin composition 1 was used, and the adhesive film obtained by the procedure of the production example of the electromagnetic wave shielding filter 1 was taken as Example 1.

(Example 2)
The transparent resin composition 2 was used, and the adhesive film obtained by the procedure of the production example of the electromagnetic wave shielding filter 2 was taken as Example 2.

(Example 3)
As a stopper layer, stopper layer preparation method 3 (formation of silicon oxynitride film by sputtering) was performed, and a phenol-formaldehyde resin (Mw = 50,000) was used as the transparent resin composition. All other conditions were the same as in Example 1. The adhesive film obtained in this manner was designated as Example 3.

Example 4
As a stopper layer, stopper layer preparation method 5 (oxidized carbonized film formation by plasma CVD method) is performed, and polydimethylsiloxane (Mw = 45,000, n = 1.43) is used as a transparent resin composition to remove the adhesive layer. Adhesive layer removal method 2: Plasma etching was used as the method, and an adhesive film obtained in the same manner as in Example 2 was used in Example 4 except for other conditions.

(Example 5)
As the stopper layer, stopper layer preparation method 6 (silicon nitride film formation by plasma CVD method) is performed, and the adhesive layer is removed by using polyvinylidene fluoride (Mw = 120,000, n = 1.42) as the transparent resin composition. The adhesive layer removing method 3: high pressure fluid removing method was used as the method, and an adhesive film obtained in the same manner as in Example 1 except for the other conditions was designated as Example 5.

(Example 6)
Stopper layer preparation method 7 (formation of silicon oxynitride carbide film by plasma CVD method) is performed as the stopper layer, and adhesive layer removal method 4: atmospheric pressure plasma etching method is used as the adhesive layer removal method, and all other conditions are performed. An adhesive film obtained in the same manner as in Example 1 was designated as Example 6.

(Example 7)
As a stopper layer, stopper layer preparation method 4 (aluminum oxide film formation by vapor deposition) is performed, and as an adhesive layer removing method, adhesive layer removing method 5: reactive etching method is used, and all other conditions are the same as in Example 1. The adhesive film obtained in this manner was designated as Example 7.

(Example 8)
As a stopper layer, stopper layer preparation method 8 (chromium oxide film formation by vapor deposition) is performed, and as an adhesive layer removing method, adhesive layer removing method 6: photoetching is used, and all other conditions are the same as in Example 1. The obtained adhesive film was referred to as Example 8.

Example 9
As the stopper layer, stopper layer preparation method 9 (ITO film formation by ion plating method) is performed, and as the adhesive layer removing method, adhesive layer removing method 7: polishing method is used, and all other conditions are the same as in Example 2. The adhesive film thus obtained was designated as Example 9.

(Example 10)
As the stopper layer, stopper layer preparation method 10 (titanium oxide film formation by sputtering method) is performed, and as the adhesive layer removing method, adhesive layer removing method 8: dry ice blasting method is used, and all other conditions are the same as in Example 2. The adhesive film obtained in this manner was designated as Example 10.

(Example 11)
As a stopper layer, a stopper layer preparation method 11 (forming a biobium oxide film by a sputtering method) was performed, and as an adhesive layer removing method, an adhesive layer removing method 9: flame treatment method was used, and all other conditions were the same as in Example 1. The adhesive film thus obtained was named Example 11.

(Example 12)
As the stopper layer, stopper layer preparation method 12 (calcium oxide film formation by sputtering method) is performed, and as the adhesive layer removing method, adhesive layer removing method 10: corona treatment is used, and all other conditions are the same as in Example 2. The obtained adhesive film was referred to as Example 12.

(Example 13)
As a stopper layer, stopper layer preparation method 13 (molybdenum oxide film formation by sputtering method) is performed, and as an adhesive layer removing method, adhesive layer removing method 11: ozone treatment is used, and all other conditions are the same as in Example 1. The obtained adhesive film was referred to as Example 13.

(Example 14)
As the stopper layer, the stopper layer preparation method 14 (tantalum oxide film formation by sputtering method) is performed, and as the adhesive layer removing method, the adhesive layer removing method 12: photolithography method is used, and all other conditions are the same as in Example 1. The obtained adhesive film was referred to as Example 14.

(Example 15)
As the stopper layer, the stopper layer preparation method 15 (ITO film formation by ion plating method) was performed, and the blackened copper was used as the conductive material. All other conditions were obtained in the same manner as in Example 1. The adhesive film was referred to as Example 15.

(Example 16)
As a stopper layer, a stopper layer manufacturing method 16 (silicon oxide carbide film formation by a sol-gel film) was performed, and a regular triangular repeating pattern was prepared instead of the lattice pattern formed in Example 1.

(Example 17)
As a removal stopper layer, stopper layer preparation method 17 (titanium oxide film formation by spray pyrolysis) was performed, and a regular hexagonal repeating pattern was prepared instead of the lattice pattern formed in Example 1.

(Example 18)
As a stopper layer, a stopper layer preparation method 18 (formation of a zirconium oxide film by a chemical solution liquid layer method) was performed, and a repetitive pattern composed of regular octagons and squares was prepared instead of the lattice pattern formed in Example 1.

Example 19
As a stopper layer, stopper layer preparation method 2 (silicon oxide film formation by ion plating method) was performed, the line width was changed from 25 μm to 35 μm, and the adhesive film obtained in the same manner as in Example 1 was implemented except for the other conditions. Example 19 was adopted.

(Example 20)
As a stopper layer, stopper layer preparation method 2 (silicon oxide film formation by ion plating method) was performed, the line width was changed from 25 μm to 12 μm, and all other conditions were carried out in the same manner as in Example 2. Example 20 was taken.

(Example 21)
As a stopper layer, stopper layer preparation method 2 (silicon oxide film formation by ion plating method) was performed, the line interval was changed from 500 μm to 800 μm, and the adhesive film obtained in the same manner as in Example 1 was implemented except for the other conditions. Example 21 was used.

(Example 22)
As a stopper layer, stopper layer preparation method 2 (silicon oxide film formation by ion plating method) was performed, the line spacing was changed from 500 μm to 250 μm, and the adhesive film obtained in the same manner as in Example 1 was implemented except for the other conditions. Example 22 was adopted.

(Example 23)
As a stopper layer, stopper layer preparation method 2 (silicon oxide film formation by ion plating method) was performed, the line thickness was changed from 25 μm to 35 μm, and all other conditions were performed in the same manner as in Example 2. Example 23 was adopted.

(Example 24)
Example 24 was performed in the same manner as in Example 1 except that a polyethylene naphthalate film (PEN film, manufactured by Teijin DuPont Films Ltd., Q65A, thickness 100 um, width 600 mm, length 5000 m) was used for the transparent plastic substrate. .

(Example 25)
Example 25 was performed in the same manner as in Example 1 except that a transparent polyimide film (manufactured by Mitsubishi Gas Chemical Company, Inc., Neoprim L-3530, thickness 100 μm) was used for the transparent plastic substrate.

(Example 26)
Example 26 was carried out in the same manner as in Example 1 except that a cyclic polyolefin film (Zeonor, manufactured by Nippon Zeon Co., Ltd.) was used for the transparent plastic substrate.

(Example 27)
Example 27 was carried out in the same manner as in Example 1 except that a norbornene resin film (manufactured by JSR, Arton) was used for the transparent plastic substrate.

(Example 28)
Example 28 was conducted in the same manner as in Example 1 except that a cured epoxy methacrylate resin (100 μm thickness) was used for the transparent plastic substrate.

(Example 29)
Example 29 was carried out in the same manner as in Example 1 except that a urethane methacrylate resin cured product (thickness: 100 μm) was used for the transparent plastic substrate.

(Example 30)
Example 30 was performed in the same manner as in Example 1 except that a polyorganosilsesquioxane-containing silicone resin substrate (manufactured by Nippon Steel Chemical Co., Ltd., HT substrate, thickness 100 μm) was used as the transparent plastic substrate. .

(Comparative Example 1)
An adhesive film obtained in the same manner as in Example 1 except that no stopper layer was provided was used as Comparative Example 1.

(Comparative Example 2)
An adhesive film obtained in the same manner as in Example 2 except that no stopper layer was provided was used as Comparative Example 2.

(Comparative Example 3)
An adhesive film obtained in the same manner as in Example 3 except that no stopper layer was provided was used as Comparative Example 3.

(Comparative Example 4)
The adhesive film obtained in the same manner as in Example 4 except that the stopper layer was not provided was used as Comparative Example 4.

(Comparative Example 5)
An adhesive film obtained in the same manner as in Example 5 except that the stopper layer was not provided was used as Comparative Example 5.

(Comparative Example 6)
An adhesive film obtained in the same manner as in Example 15 except that the stopper layer was not provided was designated as Comparative Example 6.

(Comparative Example 7)
An adhesive film obtained in the same manner as in Example 16 except that no stopper layer was provided was used as Comparative Example 7.

(Comparative Example 8)
An adhesive film obtained in the same manner as in Example 17 except that no stopper layer was provided was used as Comparative Example 8.

(Comparative Example 9)
An adhesive film obtained in the same manner as in Example 18 except that the stopper layer was not provided was used as Comparative Example 9.

(Comparative Example 10)
The adhesive film obtained in the same manner as in Example 1 except that the line width was changed from 25 μm to 50 μm and the stopper layer was not provided was used as Comparative Example 10.

(Comparative Example 11)
The adhesive film obtained in the same manner as in Example 1 except that the line width was changed from 25 μm to 35 μm and the stopper layer was not provided was used as Comparative Example 11.

(Comparative Example 12)
An adhesive film obtained in the same manner as in Example 2 was used as Comparative Example 12 except that the line width was changed from 25 μm to 12 μm and the stopper layer was not provided.

(Comparative Example 13)
An adhesive film obtained in the same manner as in Example 1 except that the line interval was changed from 500 μm to 800 μm and the stopper layer was not provided was used as Comparative Example 13.

(Comparative Example 14)
An adhesive film obtained in the same manner as in Example 1 except that the line interval was changed from 500 μm to 250 μm and no stopper layer was provided was used as Comparative Example 14.

(Comparative Example 15)
The adhesive film obtained in the same manner as in Example 2 except that the line interval was changed from 250 μm to 150 μm and the stopper layer was not provided was used as Comparative Example 15.

(Comparative Example 16)
Comparative Example 16 was an adhesive film obtained in the same manner as in Example 2 except that the line thickness was changed from 25 μm to 70 μm and the stopper layer was not provided.

(Comparative Example 17)
An adhesive film obtained in the same manner as in Example 2 except that the line thickness was changed from 25 μm to 35 μm and the stopper layer was not provided was used as Comparative Example 17.

(Comparative Example 18)
A film obtained in the same manner as in Example 1 except that a 60 μm thick filled polyethylene film (visible light transmittance of 20% or less) was used as the transparent plastic substrate, and no stopper layer was provided. It was set as Comparative Example 18.

(Comparative Example 19)
A film obtained in the same manner as in Example 1 except that an alternative layer of the adhesive 2 was formed instead of the stopper layer in Example 1 was used as Comparative Example 19.

(Comparative Example 20)
A film obtained in the same manner as in Example 2 except that an alternative layer of the adhesive 1 was formed instead of the stopper layer in Example 2 was used as Comparative Example 20.

(Comparative Example 21)
A film obtained in the same manner as in Example 3 except that an alternative layer of polyvinylidene fluoride (Mw = 120,000, n = 1.42) was formed instead of the stopper layer in Example 3 was used as Comparative Example 21. .

(Comparative Example 22)
A film obtained in the same manner as in Example 4 except that an alternative layer of phenol-formaldehyde resin (Mw = 50,000) was formed instead of the stopper layer in Example 4 was used as Comparative Example 22.

(Comparative Example 23)
Instead of the stopper layer of Example 5, polydimethylsiloxane (Mw = 45,000, n = 1.43) was used, and the adhesive film obtained in the same manner as in Example 5 was compared with Comparative Example 23. did.

  The cross-sectional shape of the composition using the adhesive film obtained as described above was measured after removing the adhesive layer, and the just edge (FIG. 3), under edge (FIG. 4), over edge (FIG. 5), over edge, taper. (FIG. 6), over-edge or reverse taper (FIG. 7) corresponds to the classification.

EMI shielding properties, visible light transmittance, invisibility, adhesion characteristics before and after heat treatment, and fading characteristics were measured. The results are shown in Tables 1 to 4.

  In addition, EMI shielding property inserts a sample between the flanges of a coaxial waveguide converter (Japan High Frequency Co., Ltd., TWC-S-024) and uses a spectroanalyzer (YHP, 8510B vector network analyzer). Measurement was performed at a frequency of 1 GHz. The visible light transmittance was measured using an average value of transmittance of 400 to 800 nm using a double beam spectrophotometer (manufactured by Hitachi, Ltd., model 200-10). Invisibility is evaluated by whether or not the geometric figure drawn with the conductive material can be recognized by visually observing the adhesive film affixed to the acrylic plate from a place 0.5 m away. A good one was recognized as a bad one. The adhesive strength was measured using a tensile tester (Tensilon UTM-4-100, manufactured by Toyo Baldwin Co., Ltd.) at a width of 10 mm, a 90 ° direction, and a peeling rate of 50 mm / min. The refractive index was measured at 25 ° C. using a refractometer (manufactured by Atago Optical Machinery Co., Ltd., Abbe refractometer).

  As is apparent from the above, the electromagnetic wave shielding filter obtained by the present invention can be used in close contact with the adherend, and therefore has no electromagnetic wave leakage and particularly good EMI shielding properties. Further, the optical properties such as visible light transmittance and invisibility are good, and the adhesive properties at a high temperature are little changed over a long period of time, and the properties are very good.

Sectional drawing of the electromagnetic wave shield filter by this invention. Sectional drawing of the electromagnetic wave shield filter by this invention. The figure which shows the process cross-section structure (just edge) after an adhesive bond layer removal process. The figure which shows the process cross-section structure (under edge) after an adhesive bond layer removal process. The figure which shows the process cross-section structure (overedge) after an adhesive bond layer removal process. The figure which shows the process cross-section structure (overedge, taper) after an adhesive bond removal process. The figure which shows the process cross-section structure (over edge, reverse taper) after an adhesive bond layer removal process. The figure which shows the outline | summary of a winding type plasma CVD apparatus. The figure which shows the outline | summary of a winding-type holo cathode type ion plating apparatus. The figure which shows the outline | summary of a winding type dual cathode type | mold sputtering apparatus. The figure which shows the outline | summary of a winding-type vapor deposition apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electromagnetic wave shielding filter 2 Transparent base material 3 Stopper layer 4 Adhesive layer 5 Conductor layer 6 Transparent resin layer

Claims (5)

  An electromagnetic wave shielding filter having transparency, wherein a stopper layer, an adhesive layer, and a conductor layer having an opening are formed on a transparent substrate, and the opening is formed in the opening of the conductor layer. An electromagnetic wave shielding filter, wherein an adhesive layer is not formed.   The electromagnetic wave shielding filter according to claim 1, wherein a transparent resin layer is further formed at least in an opening of the conductor layer. It is a manufacturing method of the electromagnetic wave shield filter according to claim 1,
On the transparent substrate, a composite having a stopper layer, an adhesive layer, and a conductor layer having an opening is prepared,
Then, the composite is subjected to an adhesive layer removing process comprising removing the adhesive layer in the opening of the conductor layer, and the method for producing an electromagnetic wave shielding filter.   A display, wherein the electromagnetic wave shielding filter according to claim 1 is disposed on an observer side of the display.   An electromagnetic wave shielding structure comprising the electromagnetic wave shielding filter according to claim 1.

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