JP2008311565A - Composite filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite filter for a display, which is used mainly for a plasma display, is excellent in production efficiency by reducing the number of lamination steps, does not easily generate color irregularities of a filter even by use for a long period of time under a high temperature or under high humidity, has a high blackness and an excellent appearance, and is provided with functions such as an electromagnetic wave shielding function, a near infrared ray absorbing function and an antiglare function. <P>SOLUTION: For the composite filter for the display, an adhesive layer containing composite tungsten oxide particulates having the near infrared ray absorbing function is formed on one surface of an electromagnetic wave shielding sheet provided with a conductive mesh layer including a blackened layer including an alloy containing nickel, copper and oxygen on one surface of a transparent resin base material, and a surface protective layer having functions such as an antireflection function and the antiglare function is formed on the other surface. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite filter disposed on the front surface of a display (image display device) such as a PDP (plasma display panel). More specifically, the present invention relates to an electromagnetic wave shielding function for shielding electromagnetic waves generated from a display, and near infrared absorption. The present invention relates to a composite filter for display having a function and a surface protection function.

  In recent years, with the advancement of functions and increase in the use of electrical and electronic equipment, electromagnetic noise interference (EMI) has increased, and electromagnetic waves are also generated in displays such as cathode ray tubes (referred to as CRT) and plasma display panels (referred to as PDP). appear. The plasma display panel is a combination of a glass having a data electrode, a fluorescent layer, and a glass having a transparent electrode, and generates a large amount of electromagnetic waves and near infrared rays when operated.

Usually, an electromagnetic wave shielding sheet is provided as a front plate on the front surface of the plasma display panel in order to shield electromagnetic waves. The shielding property of the electromagnetic wave generated from the front of the display is a standard applied to information processing devices used in home environments and residential environments specified by VCCI (Electromagnetic Interference Regulations for Information Processing Devices, etc.) at 30 MHz to 1 GHz in Japan ( It is necessary to achieve class B). In the present invention, the term “electromagnetic wave” means an electromagnetic wave in the MHz to GHz band whose frequency is centered on the above range, and does not include infrared rays, visible rays, ultraviolet rays, X-rays, etc. (for example, An electromagnetic wave having a frequency in the infrared band is called infrared rays). Furthermore, in order to make it easy to see the display image on the display, the metal mesh (line part) for shielding electromagnetic waves is difficult to see, the mesh pattern accuracy is good, the mesh is not disturbed, and it has moderate transparency (visible light transmission) ).
In addition, near infrared rays having a wavelength of 800 to 1,100 nm generated from the front surface of the plasma display also cause malfunction of other devices such as VTRs, and thus need to be shielded. In addition, there is a need for a function that blocks light (neon light) near a wavelength of 590 nm emitted from a plasma display, adjusts the hue of an image to improve color reproducibility, and further suppresses unnecessary reflection of external light. .

  In order to realize the above function, the electromagnetic wave shielding sheet and a plurality of optical filters such as a near-infrared absorption filter and an antireflection filter are laminated to prevent unnecessary electromagnetic waves and specific wavelength light generated from the image display device. It has been studied to use a plate-like composite filter that can shield and give various functions required for an image display device as a front plate of a plasma display panel (Patent Document 1). Such a composite filter is usually manufactured by laminating a large number of filters having a transparent base material on both the front and back surfaces of a glass substrate (a glass substrate for a front protective plate of the plasma display panel itself) (FIG. 1 of FIG. 1). 5, Fig. 7 and Fig. 8), the number of laminations and the number of lamination processes are large, and the cutting process requires two processes, the cutting process of the filter for the glass substrate surface and the cutting process of the filter for the back surface of the glass substrate. There was a problem above. Further, since the glass of the filter glass substrate is used as the substrate, there is a problem that both the weight and the volume are increased, and further, the filter glass substrate is easily damaged.

  Moreover, as a manufacturing method of the electromagnetic wave shielding sheet having a mesh-like metal layer among the constituent members of the composite filter, the metal foil is bonded to the transparent plastic substrate via the adhesive layer, and then the metal foil A method of forming a geometric figure by a chemical etching process (photolithography process) is known. However, according to this method, color unevenness caused by the adhesive occurs, and the roughness of the metal foil is transferred and remains uneven on the surface of the adhesive in the mesh opening. There is a disadvantage that the light is irregularly reflected and the transparency of the mesh opening is poor. Therefore, conventionally, in order to fill the roughness of the adhesive surface of the mesh opening and / or to prevent the mixing of air bubbles and make the mesh transparent, the mesh opening is previously referred to as a flattening resin. It is necessary to add a process of filling with resin and providing a planarizing layer (see FIGS. 7 and 9 of Patent Document 1).

  In the composite filter as described above, the metal mesh of the electromagnetic wave shielding sheet needs to be grounded. Therefore, the conductive mesh layer usually has a conductive layer that does not form a frame-shaped opening provided so as to surround the periphery thereof, and is generally grounded from the frame-shaped conductive layer. It is. However, in the conventional normal composite filter as described above, the metal mesh layer is sandwiched between the glass substrate and the display panel (see FIG. 5B of Patent Document 1). In addition, there was a troublesome separation of the vicinity of the grounding portion of the electromagnetic wave shielding sheet from the glass substrate again. In addition, there is a problem that even the metal layer is easily peeled off and damaged during re-peeling.

  It is also known that the metal layer included in the conductor layer is formed by a plating method into a mesh shape. Examples of the method include (1) a method of printing a conductive ink on a transparent substrate in a pattern, and metal plating on the patterned conductive ink layer (see, for example, Patent Document 2). Also, (2) a conductive ink or a photosensitive coating solution containing a chemical plating catalyst is applied on the entire surface of the transparent substrate, and the coating layer is meshed by a photolithography method, and then metal plating is performed on the mesh. The method (for example, refer nonpatent literature 1) is also mentioned. (3) A method in which a conductive treatment layer is applied on a transparent substrate, a metal plating layer is formed thereon by electrolytic plating, and then the metal plating layer and the conductive treatment layer are meshed by photolithography (for example, , See Patent Document 3).

In the case of using a PDP, in order to absorb external light to the electromagnetic wave shielding sheet and suppress external light reflection (a feeling of glare) and improve the visibility of the image on the display, A black layer is formed. This black layer is called a blackened layer and is usually formed on a metal plating layer. As the blackening layer, it is known to use, for example, metal or metal oxide plating. The metal oxide has blackness, and the blackness increases as the oxygen content increases, but there is a problem that the adhesion with the metal plating layer is deteriorated.
Good adhesion between the transparent substrate and the metal plating layer is also important for enhancing the durability of the electromagnetic wave shielding sheet. FIG. 9 (A) is a cross-sectional view schematically showing an example of the configuration of the conductor layer of the conventional electromagnetic wave shielding sheet in the form (3), and FIG. 9 (B) shows the electromagnetic wave. It is the figure which showed typically an example of the usage method of a shielding sheet. Conventionally, as shown in FIG. 9A, an alloy sputter layer, which is a base layer 131 having a conductivity necessary for plating, is formed on the transparent substrate 11 to enhance the adhesion of the conductor layer 130. ing. Then, the metal sputter layer 132 is formed by laminating a highly conductive metal having excellent electromagnetic wave shielding effect, such as copper, by a sputtering method. Thereafter, the metal plating layer 133 is formed by an electrolytic plating method with a high lamination speed, and the thickness of the highly conductive metal layer is increased. In such a case, the base layer 131 looks mainly gray, but this alone absorbs external light and does not have blackness to suppress external light reflection (a feeling of glare). , Provided on the metal plating layer 133. For example, the blackening layer 134 is formed on the metal plating layer 133 by plating.
FIG. 9B illustrates a usage pattern in which the blackening layer 134 faces the viewer 50 and the electromagnetic wave shielding sheet 135 is used on the front surface of the PDP 40. The electromagnetic wave shielding sheet 135 in which the mesh-like conductor layer 130 is formed on the transparent base material 11 has the blackening layer 134 facing the viewer 50 side, and the transparent base material 11 side facing the viewer 50 side of the front plate 60 of the PDP 40. Used by pasting.
Such a highly conductive metal having an electromagnetic wave shielding effect has poor adhesion to the transparent substrate 11 as it is. Then, the base layer 131 which has a function only for laminating | stacking copper on the transparent base material 11 is needed, and the problem that the layer structure is multilayered also has arisen.
Depending on the design of the PDP, there is a specification in which the transparent base material 11 side faces the viewer 50 side, contrary to FIG. 9B. In this case, it is necessary to form the blackening layer 134 on the transparent substrate. In this case, it is necessary to further sputter a black conductive metal thin film as the base layer 131.

  In order to meet such a purpose, an electromagnetic wave shielding transparent member in which a dark gray conductive metal thin film and a copper thin film are laminated on a transparent substrate has been developed (see, for example, Patent Document 4). In the transparent member for electromagnetic wave shielding, the gray conductive metal thin film enhances transparency and electromagnetic wave shielding performance. The conductive metal thin film is formed by sputtering, and the copper thin film is formed by sputtering, but is mainly formed by plating. Furthermore, in order to protect the copper thin film and darken the gray, a form in which a second gray conductive metal thin film is further formed on the copper thin film by a sputtering method is also shown. However, since the conductive metal thin film is gray, the blackness is insufficient, and the metallic luster remains, so that there is a problem that the antireflection effect is insufficient and external light reflection cannot be sufficiently suppressed. .

JP 2002-311843 A JP 2000-13088 A Japanese Patent Laid-Open No. 2004-241761 Japanese Patent Laid-Open No. 10-335883 JP 2006-154516 A Sumitomo Osaka Cement Co., Ltd. New Materials Division, New Materials Research Institute, New Materials Research Group, “Photoresolvable Chemical Plating Catalyst”, [online], date not listed, Sumitomo Osaka Cement Co., Ltd. Month 7 Search], Internet <URL: http: // www. socnb. com / product / hproduct / display. html>

  In Patent Document 1, an adhesive layer between the base material of the electromagnetic wave shielding sheet and the metal mesh, a flattening layer for flattening the unevenness of the metal mesh, an adhesive layer with the glass substrate, visible light and / or Or the electromagnetic wave shielding sheet containing the absorber which absorbs a specific wavelength of near infrared is disclosed. When the organic near-infrared absorber is contained in a location in contact with the glass substrate, the conductive mesh layer, or the adhesive layer between the conductive mesh layer and the base material of the electromagnetic wave shielding sheet, There was a problem that the near-infrared absorber was easily deteriorated. This is because alkali metal ions such as sodium ions derived from the glass substrate, metal atoms (or metal ions) such as copper derived from the conductive mesh, urethane bonds derived from the urethane adhesive layer, and organic dyes This is to react. Further, when an organic near-infrared absorber (pigment) is contained in a conventionally used acrylic adhesive layer that functions as an adhesive layer, an optical filter based on a reaction between the near-infrared absorber and these adjacent layers In order to simplify the layer structure, a near-infrared absorber is contained in the adhesive layer, and the layer is in contact with the metal mesh layer or the glass layer. It was difficult to put such a configuration into practical use. Furthermore, in recent years, there has been a demand for a composite filter to be directly disposed on the surface of the front panel of the plasma display panel, without interposing a glass substrate, and is necessary for a composite filter to be directly attached. Adhesion processing and flexibility were required. Furthermore, as described above, further improvements have been demanded from the viewpoint of production efficiency.

On the other hand, Patent Document 5 describes a near-infrared absorption filter for PDP using composite tungsten oxide fine particles. However, Patent Document 5 does not describe means for obtaining a composite filter having all the various functions required for a plasma display with excellent production efficiency.
Since the composite tungsten oxide fine particles are pigments, the layer in which the composite tungsten oxide fine particles are dispersed is colored. Therefore, when the near-infrared absorbing filter as described in Patent Document 5 is disposed on the front surface of the display as it is, the layer in which the composite tungsten oxide fine particles are dispersed is disposed on the front surface of the display. When it is used as a layer disposed in the vicinity, there is a problem that when the display is turned off, the front surface of the display seems to be colored with the color of the composite tungsten oxide fine particles, which is not preferred by the user. Patent Document 2 also describes that a layer in which composite tungsten oxide fine particles are dispersed is used as the high refractive index layer of the antireflection layer. In this case, the antireflection layer serving as the outermost surface layer is also used. Since the low refractive index layer is a thin film, when it is disposed on the front surface of the display, the front surface of the display appears to be colored with the color of the composite tungsten oxide fine particles. In addition, when composite tungsten oxide fine particles are contained in a layer provided as a relatively thin film such as an antireflection layer, a problem that the fine particle density in the layer increases and haze increases easily occurs.

  The present invention has been made to solve the above-mentioned problems, and is excellent in production efficiency by reducing the number of laminating processes, excellent in flexibility as a composite filter with a small number of laminating, and can reduce material costs, and Even when used for a long time, especially under high temperature and high humidity, filter color unevenness attributed to the change in spectral characteristics attributed to the deterioration of the near-infrared absorber and the color change of the adhesive hardly occurs. Provided is a composite filter for a display having at least each of an electromagnetic wave shielding function, a near-infrared absorption function, and a surface protection function with high adhesion between a conductive mesh layer and its adjacent layer, high blackness and good appearance. For the purpose.

The composite filter according to the present invention is, on one surface of a transparent resin substrate, at least one surface of an electromagnetic wave shielding sheet provided with a conductive mesh layer having a plurality of openings and a line portion surrounding and partitioning the openings. A surface protective layer having at least one function selected from the group consisting of an antireflection function, an antiglare function, and an anti-scratch function is formed on the adhesive layer and the other surface;
The conductive mesh layer has a laminated structure including a conductor layer and a blackened layer provided on at least the transparent resin substrate side of the conductor layer, and the blackened layer is formed of nickel, copper, and oxygen. A blackened layer (Ni-Cu-O blackened layer) made of an alloy containing
The pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, The composite tungsten oxide fine particles represented by 2.2 ≦ z / y ≦ 3.0) are contained.

The composite filter according to the present invention has various functions such as a near-infrared absorption function, an antiglare function, and / or an anti-scratch function in addition to the electromagnetic wave shielding function, using substantially one transparent resin substrate and both surfaces thereof. Designed to be composite.
A surface protective layer or an adhesive layer is provided directly on the conductive mesh layer surface of the electromagnetic wave shielding sheet so as to flatten the irregularities of the conductive mesh layer. As a result, the unevenness of the conductive mesh layer can be flattened, and in the case of the pressure-sensitive adhesive layer, the composite filter can be applied simultaneously in one step, so the number of steps and the flattening layer can be reduced. .
The composite tungsten oxide fine particles used as a near-infrared absorber in the present invention have high heat resistance, moisture resistance, and light resistance, and even when added to a layer that is in direct contact with the glass layer, a dye derived from sodium ions derived from the glass There is no deterioration. In addition, since the composite tungsten oxide fine particles can absorb the entire near-infrared band with a wavelength of 800 to 1,100 nm generated from the front surface of the display only by the composite tungsten oxide fine particles, the organic near-infrared absorption which is more easily deteriorated. It is not necessary to use the agent in combination. The alloy containing nickel, copper and oxygen used as a blackening layer in the present invention has high adhesion to both the transparent resin substrate and the metal layer, and has a blackness sufficient to absorb external light. have. Therefore, according to the composite filter for display of the present invention, even when used for a long time, particularly for a long time under high temperature or high humidity, the spectral characteristic change attributed to deterioration of the near-infrared absorber and the adhesive Color unevenness of the filter attributed to discoloration hardly occurs. In order to prevent deterioration of the near-infrared absorber, a near-infrared absorbing layer is formed from a glass substrate such as a display surface, a conductive mesh layer, or an adhesive layer between the conductive mesh layer and the base material of the electromagnetic shielding sheet. There is no need to isolate. For this reason, it has an electromagnetic shielding function, a near infrared absorption function, and a surface protection function with high blackness and excellent appearance, such as a composite filter for a display according to the present invention, and is produced by reducing the number of lamination processes. It has become possible to put into practical use a structure that is excellent in efficiency, thin in thickness with a small number of layers, excellent in flexibility as a composite filter, and can reduce material costs.
In the composite filter for display according to the present invention, since the layer in which the composite tungsten oxide fine particles are dispersed is disposed so as to be on the back side of the electromagnetic wave shielding sheet when viewed from the observation side when the front surface of the display is attached, The conventional problem that the front surface of the display appears to be colored and is not preferred by the user when the display is turned off without being tinted with fine particles can be solved. In addition, when the composite tungsten oxide fine particles are contained in a layer provided as a relatively thin film such as an antireflection layer, there is a problem that the fine particle density in the layer increases and haze increases. Thus, when it is made to contain in the resin layer which serves as an adhesive layer, since a layer is thick compared with an antireflection layer, there also exists a merit that it can control that haze becomes high.

  In the composite filter for display according to the present invention, it is preferable that a part of the peripheral edge of the conductive mesh layer is exposed. In the case of such an embodiment, it is not necessary to perform a peeling process for grounding, etc., and it is a single process for applying a composite filter or forming a surface protective layer, and flattening and securing a grounding area around the conductive mesh layer. The number of steps can be further reduced and productivity can be improved.

  Among preferred embodiments of the composite filter according to the present invention, as a first embodiment, the surface of the electromagnetic shielding sheet on the side of the conductive mesh layer, directly without any other layer, and an adhesive layer, A surface protective layer having at least one function selected from the group consisting of an antireflection function, an antiglare function, and an anti-scratch function on the other surface of the electromagnetic wave shielding sheet that does not have the conductive mesh layer of the transparent resin substrate. And the conductive mesh layer in the electromagnetic wave shielding sheet includes an embodiment in which the surface on the transparent resin base material side is subjected to Ni—Cu—O blackening treatment.

  Of the preferred embodiments of the composite filter according to the present invention, as a second embodiment, the surface of the electromagnetic shielding sheet on the side of the conductive mesh layer is composed of an antireflection function, an antiglare function, and an abrasion resistance function. A surface protective layer having one or more functions selected from the above, a pressure-sensitive adhesive layer is formed on the other surface of the electromagnetic wave shielding sheet that does not have a conductive mesh layer of the transparent resin substrate, and As for the electroconductive mesh layer in the said electromagnetic wave shielding sheet, embodiment by which the surface on the opposite side to the said transparent resin base material side is Ni-Cu-O blackening process is mentioned.

In the composite filter for display according to the present invention, it is preferable that the transparent resin substrate, the surface protective layer, and / or the pressure-sensitive adhesive layer contain an ultraviolet absorber. In the case of such an embodiment, in addition to the adhesive layer containing the composite tungsten oxide fine particles, the transparent resin base material and / or the surface protective layer has an ultraviolet absorbing function. Can prevent deterioration and deterioration. Moreover, in the composite filter for displays which concerns on this invention, it is preferable that the said adhesive layer contains a neon light absorber and / or a color correction pigment | dye. With the above configuration, it is possible to reduce the step of attaching the functional filter composed of each functional layer and the base material, and thus the production efficiency is excellent. In addition, the thickness is reduced with a small number of layers, excellent flexibility as a composite filter, winding is possible, and material costs can be reduced.
Moreover, when it has a layer structure like this invention, there exists a merit that interface reflection can be suppressed by the number of layers reduction.

  In the composite filter for display according to the present invention, the average dispersed particle size of the composite tungsten oxide fine particles is preferably 800 nm or less from the viewpoint of high transmittance in the visible region and low haze.

  In the composite filter for display according to the present invention, the composite tungsten oxide fine particles include one or more crystal structures of hexagonal crystal, tetragonal crystal, and cubic crystal from the viewpoint of improving the durability of optical characteristics. preferable.

  In the composite filter for a display according to the present invention, the M element of the composite tungsten oxide fine particles is a Cs (cesium) element, and the composite tungsten oxide fine particles have a hexagonal crystal structure, It is preferable from the point of durability improvement.

  In the composite filter for display according to the present invention, the surface of the composite tungsten oxide fine particles is coated with an oxide containing one or more elements selected from Si, Ti, Zr, and Al. It is preferable from the viewpoint of improving the durability of optical characteristics.

As one embodiment of the present invention, the conductive mesh layer is formed from the side close to the transparent resin substrate, the Ni-Cu-O blackening layer, a metal thin film as a conductor layer formed by vapor phase film formation. These layers and the metal layer may have a stacked structure in which they are stacked in this order. The adhesion between the transparent resin substrate and the metal layer can be improved by the metal thin film layer.
Moreover, as another embodiment, the conductive mesh layer is formed from the side close to the transparent resin base material, a metal thin film layer as a conductor layer formed by the vapor phase film formation, the metal layer, and the The Ni—Cu—O blackening layer may have a stacked structure in which these layers are stacked in this order.
The Ni—Cu—O blackening layer is preferably a thin film layer formed by vapor deposition. The thickness of the Ni—Cu—O blackening layer is preferably 80 to 300 mm. The metal layer is preferably a copper plating layer from the viewpoint of obtaining excellent electromagnetic shielding properties.

As one embodiment of the present invention, when the copper plating layer represents the abundance ratio of crystal planes parallel to the surface of the copper plating layer as a plane index peak ratio of crystal planes specified by X-ray diffraction measurement Further, the ratio of the (200) plane strength to the (111) plane strength can be 50% or more.
As another embodiment, when the copper plating layer represents the abundance ratio of crystal planes parallel to the surface of the copper plating layer as a plane index peak ratio of crystal planes specified by X-ray diffraction measurement Furthermore, the ratio of the (220) plane strength to the (111) plane strength can be 50% or more.
Furthermore, as another embodiment, when the copper plating layer represents an abundance ratio of crystal planes parallel to the surface of the copper plating layer as a plane index peak ratio of crystal planes specified by X-ray diffraction measurement Furthermore, the ratio of the total strength of the (200) plane and the (220) plane to the (111) plane strength can be 70% or more.

The method for producing a composite filter for display according to the present invention includes an electromagnetic wave shielding sheet having a conductive mesh layer having at least a plurality of openings and a line portion surrounding and partitioning on one surface of a transparent resin substrate. A surface protective layer having one or more functions selected from the group consisting of an antireflection function, an antiglare function, and an anti-scratch function is formed on one surface and an adhesive layer on the other surface. The conductive mesh layer has a laminated structure including a metal layer as a conductor layer and a blackened layer provided on at least the transparent resin substrate side of the metal layer, and the blackened layer includes nickel and copper. It is a blackening layer (Ni-Cu-O blackening layer) made of an alloy containing oxygen, and the pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, Rare earth elements, Mg, Zr, Cr, Mn, Fe, u, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, One or more elements selected from Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), which is a method for producing a composite filter for display, comprising the composite tungsten oxide fine particles. On the other hand, a step of forming a metal plating layer as the metal layer on one surface of the transparent resin substrate, from an alloy containing nickel, copper and oxygen by sputtering using a Ni—Cu alloy as a target in the presence of oxygen gas A blackening layer (Ni-Cu-O blackening layer) is formed And a step of forming another layer to be included in the conductor layer in a predetermined order to form a non-mesh structure having a laminated structure including a metal plating layer and a Ni—Cu—O blackening layer After forming the conductor layer, the method includes a step of etching the conductor layer into a predetermined mesh shape, a step of forming a surface protective layer, and a step of forming an adhesive layer.
The metal layer can be suitably formed by copper plating by an electrolytic plating method.
The blackening layer can be suitably formed by a sputtering method (reactive sputtering) in which an oxygen gas is supplied using a Ni—Cu alloy as a target.

  The composite filter for display of the present invention has at least each function of an electromagnetic wave shielding function, a near-infrared absorption function, and a surface protection function, and is excellent in production efficiency by reducing the number of lamination processes, and is thin with a small number of laminations. In addition, the adhesiveness between the conductive mesh layer and the adjacent layer is high, the composite filter is excellent in flexibility, the material cost can be reduced, and the interface reflection can be suppressed by reducing the number of layers. Furthermore, the composite filter for display according to the present invention is attributed to the change in spectral characteristics and the discoloration of the adhesive attributed to the deterioration of the near-infrared absorber even when used for a long time, particularly for a long time under high temperature or high humidity. The color unevenness of the filter is hardly generated, the filter surface is not colored, the blackness is excellent, the external light reflection is small, and the appearance when installed on the front surface of the plasma display is excellent.

The composite filter for a display according to the present invention is an electromagnetic wave shielding sheet provided with a conductive mesh layer having at least a plurality of openings and a line portion surrounding and partitioning on one surface of the transparent resin substrate. A surface protective layer having one or more functions selected from the group consisting of an adhesive layer on the surface and an antireflection function, an antiglare function, and an anti-scratch function on the other surface;
The conductive mesh layer is a blackened layer provided on a conductive layer such as a metal layer or a conductive ink layer and at least the transparent resin substrate side (also on the surface protective layer side, that is, the observer side) of the conductive layer. And the blackening layer is a blackening layer (Ni-Cu-O blackening layer) made of an alloy containing nickel, copper, and oxygen,
The pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, The composite tungsten oxide fine particles represented by 2.2 ≦ z / y ≦ 3.0) are contained.
The method for producing a composite filter for display according to the present invention includes an electromagnetic wave shielding sheet having a conductive mesh layer having at least a plurality of openings and a line portion surrounding and partitioning on one surface of a transparent resin substrate. A surface protective layer having one or more functions selected from the group consisting of an adhesive layer on one surface and an antireflection function, an antiglare function, and an anti-scratch function on the other surface,
The conductive mesh layer has a laminated structure including a metal layer as a conductor layer and a blackened layer provided on at least the transparent resin substrate side of the metal layer, and the blackened layer is made of nickel, It is a blackened layer (Ni-Cu-O blackened layer) made of an alloy containing copper and oxygen,
The pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), which is a method for producing a composite filter for display containing composite tungsten oxide fine particles,
A step of forming a metal plating layer as the metal layer on one surface of the transparent resin base material with respect to the transparent resin base material, nickel and copper by sputtering with a Ni—Cu alloy target in the presence of oxygen gas And a step of forming a blackening layer (Ni-Cu-O blackening layer) made of an alloy containing oxygen and a step of forming another layer to be included in the conductor layer in a predetermined order, After forming a non-mesh conductor layer having a laminated structure including a metal plating layer and a Ni—Cu—O blackening layer, etching the conductor layer into a predetermined mesh shape, forming a surface protective layer And a step of forming a pressure-sensitive adhesive layer.

The layer structure of the composite filter for plasma display according to the present invention will be described with reference to the drawings.
A sectional view of an example of a composite filter according to the present invention is conceptually shown in FIG. In the cross-sectional views of FIG. 1 and subsequent figures, for ease of explanation, the thickness direction (vertical direction in the figure) is greatly enlarged and exaggerated from the scale in the plane direction (horizontal direction in the figure). The composite filter 1 shown in FIG. 1 has an adhesive layer 20 on one surface and an antireflection function on the other surface of an electromagnetic wave shielding sheet 10 having a conductive mesh layer 16 on one surface of a transparent resin substrate 11. A surface protective layer 30 having at least one function selected from the group consisting of an antiglare function and a scratch resistance function is formed. Here, the conductive mesh layer 16 includes a blackening layer 13 and a copper sputter layer 14 as a metal thin film layer formed by vapor deposition (in the present invention, copper, copper alloy, or copper oxide). A film formed from a material by sputtering is called a copper sputter layer), and has a laminated structure including a copper plating layer 15 as a metal layer (in the main embodiment of the present invention, a metal layer is In order to form by plating, hereinafter, the term “metal plating layer is used as appropriate” as a vocabulary representing the metal layer), the blackening layer 13 is a blackening layer (Ni—Cu) made of an alloy containing nickel, copper and oxygen. -O blackening layer), and the pressure-sensitive adhesive layer 20 has the general formula MxWyOz (where the M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, u, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, One or more elements selected from Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3 .0) is contained. Furthermore, the composite filter 1 according to the present invention is formed such that the pressure-sensitive adhesive layer 20 or the surface protective layer 30 flattens the unevenness of the conductive mesh layer on the conductive mesh layer 16. Furthermore, in the composite filter 1 according to the present invention, as shown in FIG. 1, the pressure-sensitive adhesive layer 20 or the surface protective layer 30 exposes a part 17 of the peripheral portion of the conductive mesh layer instead of the entire surface on the conductive mesh layer 16. It is preferable that it is partially formed in a pattern by intermittent coating or intermittent bonding so as to make it happen.
If the composite filter for display according to the present invention is disposed on the front surface of a display panel such as a PDP, even if it is directly attached on the front glass substrate of the display panel body, it is applied to a transparent substrate such as another glass. It may be disposed on the front surface of the display panel as a front plate after being attached. Moreover, you may have an optical function etc. separately through the adhesive layer 20. FIG.

  FIG. 1 is a first embodiment of a preferred embodiment of a composite filter according to the present invention, in which an adhesive layer 20 is formed on the surface of the electromagnetic shielding sheet 10 on the conductive mesh layer 16 side, and Surface having at least one function selected from the group consisting of an antireflection function, an antiglare function, and a scratch resistance function on the other surface of the electromagnetic wave shielding sheet 10 that does not have the conductive mesh layer 16 of the transparent resin substrate 11 The protective layer 30 is formed, and the conductive mesh layer 16 in the electromagnetic wave shielding sheet is formed by vapor deposition as the blackening layer 13 and the conductor layer from the side close to the transparent resin substrate 11 side. A copper sputter layer 14 and a copper plating layer 15 which are the formed metal thin films are formed.

  FIG. 2 is a second embodiment among the preferred embodiments of the composite filter according to the present invention, and the surface of the electromagnetic wave shielding sheet 10 that does not have the conductive mesh layer 16 of the transparent resin base material 11. Surface protection having an adhesive layer 20 and having at least one function selected from the group consisting of an antireflection function, an antiglare function, and an abrasion resistance function on the surface of the electromagnetic wave shielding sheet on the conductive mesh layer 16 side. The conductive mesh layer 16 in the electromagnetic wave shielding sheet is a metal thin film formed by vapor-phase film formation as a conductor layer from the side close to the transparent resin substrate 11 side. A copper sputter layer 14, a copper plating layer 15, and a blackening layer 13 are formed.

According to the composite filter for display of the present invention, using substantially one transparent resin substrate 11 and both surfaces thereof, in addition to the electromagnetic wave shielding function, the near infrared ray absorbing function, further, the antireflection function, the antiglare function, And / or it is designed to combine various functions such as a scratch resistance function. Therefore, the optical function developing part does not take a laminated structure having a transparent base material in each piece and a plurality of transparent base materials (about 2 to 3 layers) in total, as in the past. Therefore, the transparent base material of the optical filter which was conventionally contained in multiple numbers, and the adhesive bond layer for bonding them together can be reduced. As a result, the composite filter for display of the present invention can be reduced in material cost, and can be reduced in thickness with a small number of layers, and thus has excellent flexibility as a composite filter. Moreover, when it has a layer structure like this invention, there exists a merit that interface reflection can be suppressed by the number of layers reduction.
Furthermore, without providing a separate flattening layer on the surface of the conductive mesh layer 16 of the electromagnetic wave shielding sheet 10, in the case of the embodiment of FIG. 1, the pressure-sensitive adhesive layer 20 is directly flattened so that the unevenness of the conductive mesh layer is flattened. Therefore, the pressure-sensitive adhesive layer 20 that also has a function of flattening the mesh surface of the electromagnetic wave shielding sheet 10 serves as an affixing surface of the composite filter. ) Directly. Further, in the case of the embodiment of FIG. 1, a part 17 of the exposed peripheral edge portion of the conductive mesh layer 16 can be used as it is as a grounding region. As described above, the present invention can simultaneously perform the bonding process of the composite filter, the flattening of the conductive mesh layer, and the grounding area around the periphery of the conductive mesh layer in one process. The formation layer can be reduced.
In addition, since the composite filter for display according to the present invention has optimized the arrangement of each layer, there is no need for a step of pasting the base films in the optical filter and the electromagnetic wave shielding sheet as in the past, and the production efficiency is improved. Excellent.

The composite tungsten oxide fine particles used as a near-infrared absorber in the present invention have high heat resistance, moisture resistance, and light resistance. In particular, the composite tungsten oxide fine particles include a metal layer of a conductive mesh, a glass layer of a display front plate, or an adhesive layer having a urethane bond, which has been a cause of deteriorating conventional organic near infrared absorbing dyes. Even if it is contained in the contacting layer, characteristic deterioration due to reaction with these layers hardly occurs. In addition, since the composite tungsten oxide fine particles can absorb the entire near-infrared band with a wavelength of 800 to 1,100 nm generated from the front surface of the display only by the composite tungsten oxide fine particles, the organic near-infrared absorption which is more easily deteriorated. It is not necessary to use the agent in combination. The alloy containing nickel, copper and oxygen used as a blackening layer in the present invention has high adhesion to both the transparent resin substrate and the metal layer, and has a blackness sufficient to absorb external light. have. The conductive mesh layer is typically formed by etching a metal foil, and is significant in the electromagnetic wave shielding function. However, when the conductive mesh layer is formed on the transparent resin base material, if a metal layer is formed by a plating method, an adhesive for attaching the metal foil becomes unnecessary. In particular, when it is desired to form an extremely thin copper layer (for example, 5 μm or less), handling of the copper foil in the process of laminating the copper foil is very troublesome and easily damaged. A thin copper plating layer can be easily formed. Therefore, according to the composite filter for display of the present invention, even when used for a long time, particularly for a long time under high temperature or high humidity, the spectral characteristic change attributed to deterioration of the near-infrared absorber and the adhesive Color unevenness of the filter attributed to discoloration hardly occurs. In order to prevent deterioration of the near-infrared absorber, a near-infrared absorbing layer is formed from a glass substrate such as a display surface, a conductive mesh layer, or an adhesive layer between the conductive mesh layer and the base material of the electromagnetic shielding sheet. There is no need to isolate. Further, there is no problem that the opening from which the metal foil is removed becomes a rough surface and irregular reflection of light occurs. For this reason, it has an electromagnetic shielding function, a near infrared absorption function, and a surface protection function with high blackness and excellent appearance, such as a composite filter for a display according to the present invention, and is produced by reducing the number of lamination processes. It has become possible to put into practical use a structure that is excellent in efficiency, thin in thickness with a small number of layers, excellent in flexibility as a composite filter, and can reduce material costs.
In the composite filter for display according to the present invention, since the layer in which the composite tungsten oxide fine particles are dispersed is disposed so as to be on the back side of the electromagnetic wave shielding sheet when viewed from the observation side when the front surface of the display is attached, The conventional problem that the front surface of the display appears to be colored and is not preferred by the user when the display is turned off without being tinted with fine particles can be solved. In addition, when the composite tungsten oxide fine particles are contained in a layer provided as a relatively thin film such as an antireflection layer, there is a problem that the fine particle density in the layer increases and haze increases. Thus, when it is made to contain in the resin layer which serves as an adhesive layer, since a layer is thick compared with an antireflection layer, there also exists a merit that it can control that haze becomes high.
Hereinafter, the electromagnetic wave shielding sheet, the pressure-sensitive adhesive layer, and the surface protective layer will be described in order for the composite filter used in the present invention.

1. Electromagnetic wave shielding sheet "Layer structure of electromagnetic wave shielding sheet"
As the electromagnetic wave shielding sheet used in the present invention, a sheet provided with a conductive mesh layer having at least a plurality of openings and a line portion surrounding and partitioning on one surface of the transparent resin substrate is used.
An example of the electromagnetic wave shielding sheet used in the present invention is shown in FIG. FIG. 3A is a plan view of an example of the electromagnetic wave shielding sheet used in the present invention, and FIG. 3B is a cross-sectional view of an example of the electromagnetic wave shielding sheet used in the present invention. However, in FIG. 3B, for the sake of illustration and ease of viewing, the scale in the thickness direction is made larger than the scale in the in-plane direction, and the width of the line portion is larger than the width of the opening. Is exaggerated.
The conductive mesh layer in the electromagnetic wave shielding sheet 10 used in the present invention is other than the mesh region 101 in the plane direction as in the conductive mesh layer 16 conceptually illustrated in the plan view of FIG. The layer having the non-mesh region 102 in at least a part of the peripheral edge of the mesh region is more preferable in terms of easy grounding.
The mesh area 101 has a size and shape that can cover the entire image display area of the applied display, and always includes a portion 70 that faces the image display area of the applied display. The outer edge portion that is an area outside the portion 70 that faces the image display area of the display may include the mesh area 101 or may include only the non-mesh area 102. The non-mesh region 102 usually has the same layer structure as the mesh region 101 but does not form an opening, and is provided for easy grounding when installed on a display as a grounding region. It is done. The grounding region basically does not require a mesh, but a mesh composed of openings may be present for the purpose of preventing warpage of the grounding region. The grounding area (corresponding to the non-mesh area 102 in the example of FIG. 3A) has an influence on the image display which is the outer edge part which is an area outside the part 70 facing the image display area of the normal rectangular display. In many cases, the frame is provided in a frame shape around the four sides, but may be provided in a part of the periphery of the mesh-like region 101, or may be provided on only three sides, two sides, or one side. Form may be sufficient.

Further, as shown in FIG. 3B, the electromagnetic wave shielding sheet 10 used in the present invention is a pressure-sensitive adhesive layer 20 so as to flatten the unevenness of the conductive mesh layer on the conductive mesh layer 16 later. Or the surface protection layer 30 is installed. As shown in FIG. 3 (A), the pressure-sensitive adhesive layer 20 or the surface protective layer 30 usually covers at least the portion 70 facing the image display area of a normal quadrangular display, and the conductive mesh layer. The non-mesh region 102 is preferably laminated so as to expose a part of the peripheral portion, and is preferably provided so that the grounding region is exposed in a frame shape around the four sides. In the example of FIG. 3 (B), the conductive mesh layer 16 has a blackened layer 13, a copper sputtered layer 14 as a metal thin film formed by vapor deposition, from the side close to the transparent resin substrate 11, and The copper plating layer 15 as a metal layer has a layer structure in which the layers are stacked in this order.
Moreover, the electromagnetic wave shielding sheet 10 used in the present invention has an adhesive layer (see FIG. 5) for attaching the conductive mesh layer 16 to the transparent resin substrate 11 between the conductive mesh layer 16 and the transparent resin substrate 11. (Not shown). In addition to the blackening layer 13, the conductive mesh layer 16 may include other layers such as a rust prevention layer. Moreover, the electromagnetic wave shielding sheet used in the present invention may be formed by further laminating a non-conductive layer on the front and back surfaces of the conductive mesh layer. Examples of the layer that does not have conductivity include a rust preventive layer and a blackened layer that do not have conductivity. Even if it is a rust prevention layer, a blackening layer, etc., as long as it has electroconductivity, it is contained in the electroconductive mesh layer 16 in this invention. The non-conductive layer further laminated on the front and back surfaces of the conductor layer is integrated with the conductive mesh layer to form a mesh-like region and a grounding region.

"Modification of layer structure of electromagnetic shielding sheet"
4A to 4C are cross-sectional views schematically showing another example of the layer configuration of the conductor layer according to the present invention.
FIG. 4A shows a conductive layer in which a blackening layer 13 according to the present invention, a copper sputtered layer 14, a copper plating layer 15, and a second blackening layer 80 according to the present invention are laminated in this order on a transparent resin substrate 11. The mesh layer 16B is illustrated (hereinafter referred to as a second blackened layer, and the second blackened layer 80 will be described later).
FIG. 4B shows a conductive mesh layer 16C in which the blackening layer 13, the copper sputtered layer 14, the copper plating layer 15, and the known blackening layer 81 according to the present invention are laminated on the transparent resin substrate 11 in this order. It is illustrated (hereinafter referred to as a known blackened layer, and a known blackened layer 81 will be described later).
In FIG. 4C, a base layer (usually a Ni—Cr alloy layer) 18, a copper sputter layer 14, a copper plating layer 15, and a blackening layer 13 according to the present invention are laminated in this order on the transparent resin base material 11. A conductive mesh layer 16D is shown.
In the present invention, the copper sputter layer 14 can be omitted. Although not shown in the drawings, on the transparent resin base material, at least a Ni—Cr alloy underlayer, a copper sputter layer, a blackening layer according to the present invention, and a copper plating layer are laminated in this order. It may be a body layer. Furthermore, other layers such as a rust prevention layer may be formed on each of the conductor layers.

As shown in FIG. 1, the position of the blackened layer in the conductive mesh layer is usually determined by whether the blackened layer 13 is provided on the side of the conductive mesh layer 16 that contacts the transparent resin base material 11 (this is the As shown in FIG. 2, a blackening layer 13 is provided on the side of the conductive mesh layer 16 opposite to the side on which the transparent resin base material 11 is in contact (this is called the reverse specification). Sometimes).
Regardless of the forward rotation specification or the reverse rotation specification, when the electromagnetic wave shielding sheet is in use, the side on which the blackened layer of the electromagnetic wave shielding sheet is provided is the observer in order to exhibit the function of absorbing external light by the blackened layer. It is arranged to face. The display device side can select whether or not the blackening layer is present, as required.

  In addition, although the electromagnetic wave shielding sheet | seats shown in figure are all sheet-fed, in this invention, the electromagnetic wave shielding sheet | seat is a division | segmentation more than two sheet | seat sheets in the stage before installing in the front surface of a display. The state of the continuous strip | belt-shaped sheet | seat containing may be sufficient. Preferably, in the stage until the later-described pressure-sensitive adhesive layer and surface protective layer are laminated on the electromagnetic wave shielding sheet, the electromagnetic wave shielding sheet, the pressure-sensitive adhesive layer, and the surface protective layer can all be processed in the form of a continuous belt-like sheet. It is preferable for ensuring high productivity.

(1) Transparent resin base material The transparent resin base material is a part of the layer constituting the electromagnetic wave shielding sheet, and is a layer serving as a base material for laminating a conductive mesh layer through an adhesive layer as necessary. is there.
The transparent resin base material 11 is a layer for reinforcing the conductive mesh layer having a low mechanical strength, and is one of the layers to which an ultraviolet absorbing function can be added if necessary. Accordingly, as the transparent resin base material, it is possible to select a transparent resin base material that appropriately considers performance such as heat resistance as long as it has an ultraviolet absorbing ability as well as mechanical strength and light transmittance. As a specific example of such a transparent resin base material, a sheet (or film, the same applies hereinafter) made of an organic material such as a resin can be given. The higher the transparency of the transparent resin substrate, the better. However, the light transmittance in the visible light region of 380 to 780 nm is preferably 70% or more, more preferably 80% or more. The light transmittance can be measured using a spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation) and a value measured in the air at room temperature.

  Examples of the transparent resin used as the material for the transparent resin substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer Polyester resins such as nylon 6, polyamide resins such as nylon 6, polyolefin resins such as polypropylene, polymethylpentene and cycloolefin polymers, acrylic resins such as polymethyl methacrylate, styrene such as polystyrene and styrene-acrylonitrile copolymers Resin, cellulose resin such as triacetyl cellulose, imide resin, polycarbonate resin and the like.

  These resins are used alone or as a plurality of types of mixed resins (including polymer alloys), and the layer structure of the transparent substrate is used as a single layer or a laminate of two or more layers. In the case of a resin film, a uniaxially stretched or biaxially stretched film is more preferable in terms of mechanical strength. Moreover, you may add additives, such as a ultraviolet absorber, a filler, a plasticizer, an antistatic agent, in these resins suitably as needed.

The thickness of the transparent resin substrate may basically be selected according to the use and is not particularly limited, but is usually 12 to 1,000 μm, preferably 50 to 500 μm, more preferably 50 to 200 μm. Within such a thickness range, the mechanical strength is sufficient, warping, slackening, breakage, etc. are prevented, and it is easy to supply and process in a continuous belt shape.
In the present invention, the transparent resin base material is referred to as including a resin plate in addition to the resin sheet (including the resin film). However, from the viewpoint of reducing the total thickness by stacking near-infrared (NIR) absorption, neon light absorption and color correction for each filter film, the transparent resin substrate should be thin. preferable.

  In this respect, the transparent resin film is preferably a transparent resin film rather than a resin plate. Among these resin films, polyester resin films such as polyethylene terephthalate and polyethylene naphthalate are preferable in terms of transparency, heat resistance, cost, and the like, and more preferably a biaxially stretched polyethylene terephthalate film.

In the present invention, when the transparent resin base material has an ultraviolet absorbing function, the transparent resin base material is prepared by kneading an ultraviolet absorbent into a film of the transparent resin base material or the transparent resin base material. As a part of the constituent layers of the material, a surface coat layer containing an ultraviolet absorber is provided on the surface, or both are used in combination. In addition, the surface on which the surface coat layer is provided may be either one side or both sides of the front and back surfaces.
Further, in the case of forming the surface coating layer containing an ultraviolet absorber on the surface protective layer forming surface side in view of providing a surface protective layer on one surface of the transparent resin substrate, the surface coating layer and the surface The protective layer may also be used as a surface protective layer.

As the ultraviolet absorber, for example, a known compound composed of an organic compound such as benzotriazole or benzophenone, an inorganic compound composed of particulate zinc oxide, cerium oxide or the like can be used.
Moreover, the surface coat layer (ultraviolet absorption layer) containing an ultraviolet absorber may be formed by applying a composition obtained by adding such an ultraviolet absorber to a binder resin by a known method. As binder resin, thermoplastic resin such as polyester resin, polyurethane resin, acrylic resin, thermosetting resin or ionizing radiation curable resin composed of monomers such as epoxy, acrylate and methacrylate, prepolymer, etc. Examples thereof include curable resins such as curable urethane resins.

  In addition, a known additive, for example, a filler, a plasticizer, an antistatic agent, or the like may be added to the resin of the transparent resin base as necessary within the range not departing from the gist of the present invention. it can.

  The transparent resin base material is appropriately subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, preheat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, etc. You may go.

(2) Conductive mesh layer The conductive mesh layer 16 is a layer that can have an electromagnetic wave shielding function by having conductivity, and is itself an opaque but mesh-like shape having a large number of openings, It is a layer that achieves both electromagnetic shielding performance and light transmittance. Moreover, in the typical embodiment of this invention, the electroconductive mesh layer 16 contains the copper plating layer 15 and the blackening layer 13 as a main layer, and also depending on the case, the copper sputter layer 14 and the copper plating layer 15 are further included. A second blackening layer 80 (see FIG. 4A), a known blackening layer 81 (see FIG. 4B), and a rust prevention layer may be further formed thereon.

(Metal plating layer)
The metal plating layer 15 is formed of a material having excellent conductivity, and is a representative example suitable as a main portion in which the electromagnetic wave shielding function is expressed in the conductive mesh layer 16. Other layers laminated on the upper or lower side of the metal plating layer are also conductive, and when integrated as an excellent conductor, the main part that exhibits the electromagnetic wave shielding function including those other layers Is configured. For example, in the example shown in FIG. 1, the blackened layer 13 made of a Ni—Cu—O-based alloy and the copper sputter layer 14 as a metal thin film layer formed by vapor deposition have conductivity. Therefore, it constitutes a main part where the electromagnetic wave shielding function is exhibited together with the copper plating layer 15 as the metal plating layer.
As a plating method for forming the metal plating layer, either electrolytic plating or electroless plating may be performed, but from the viewpoint of productivity, it is preferable to perform electrolytic plating with a high film growth rate.

In the present invention, the preferred form of the conductor layer is a metal layer, and a particularly preferred example is a metal plating layer. The metal forming the metal plating layer is a highly conductive metal and excellent in electromagnetic wave shielding properties. Is preferably used, and the resulting plating layer is referred to as a copper plating layer 15. In the present invention, the copper plating layer 15 is preferably formed by electrolytic plating after the surface of the copper sputter layer 14 or another layer is formed. By forming the copper plating layer 15 by the electrolytic plating method, an adhesive for bonding the copper foil becomes unnecessary. In particular, when it is desired to form an extremely thin copper layer (for example, 5 μm or less), handling of the copper foil in the process of laminating the copper foil is very troublesome and easily damaged. A thin copper plating layer can be easily formed. In the present invention, the copper plating layer 15 is typically composed of a single copper, but if it is mainly composed of copper and has crystal orientation described later, gold, silver, platinum, copper, aluminum Other metals such as tin, iron, nickel, and chromium may be included. When the copper plating layer 15 is a mixture of copper and another metal or a copper alloy, the copper content is preferably 90% by weight or more, and 95% by weight or more of the total metal components. Further preferred.
The thickness of the copper plating layer 15 is preferably as thin as possible within a range where sufficient shielding performance and physical properties that do not break during the processing process can be obtained. However, the thickness of the entire conductor layer including the copper plating layer 15 is not limited. It is determined in consideration of the thickness of other layers within the range. From this viewpoint, the thickness of the copper plating layer 15 included in the conductive mesh layer 16 is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. Further, the thickness of the copper plating layer 15 is preferably 1 μm or more, and more preferably 2 μm or more. The blackening layer 13 according to the present invention is particularly excellent in adhesion with copper as described above.

(Blackening layer)
In the present invention, as the blackening layer 13, a compound composed of three elements of Ni—Cu—O (hereinafter referred to as (Ni—Cu—O) compound) is used. In order to absorb the external light to the electromagnetic wave shielding sheet 10 and improve the visibility of the image on the display, the transparent resin base is used directly as shown in FIGS. 4A and 4B or via another layer as shown in FIG. 4C. A blackening layer 13 is formed on the material 11. Although the formation method of the blackening layer 13 is not specifically limited, It can form suitably by vapor phase film-forming, such as a sputtering method and a vacuum evaporation method. Sputtering is particularly preferred because of its high deposition rate and excellent adhesion.
In the sputtering method, Ni—Cu (nickel-copper alloy) is used as a target, and argon is ionized by applying a high voltage while supplying a desired amount of oxygen gas. 11 is deposited to form a blackened layer 13. The blackening layer 13 has excellent adhesion to the transparent resin substrate 11, a copper sputter layer 14, which will be described later, and the copper plating layer 15 described above, and has a function as a base layer. Therefore, the step of forming the base layer is omitted. You can also. Since the blackening layer 13 according to the present invention has high blackness, it can absorb external light and suppress external light reflection (glare feeling).

  The thickness of the blackening layer 13 is not particularly limited, but a range of about 80 to 1000 mm is applicable, but considering practical conditions (productivity, performance, etc.), 80 mm (= 8 nm) The thickness is preferably 300 mm (= 30 nm) or less, more preferably 120 mm or more and 160 mm or less. If it is less than 80 mm, the light transmittance is high, the metal color of the copper sputter layer 14 is remarkable and it is difficult to obtain a sufficient degree of blackening, and if it exceeds 1000 mm, it seems that there is light interference due to the thickness, It is not a good idea if it is thick. In addition, it is a feature of the present invention that the film has a blackness for expressing a function as a blackening layer even if the film is about the same as or thinner than the conventional film thickness of 0.001 μm to 1 μm. In addition, the thickness of the blackening layer based on this invention is the conversion value converted with the analytical curve based on the numerical value measured using a fluorescent X ray measuring apparatus.

  The black density of the blackened layer is preferably 0.6 or more. In addition, the measurement method of the black density is set to the density standard ANSIT as the observation viewing angle 10 degrees, the observation light source D65, and the illumination type using GRETAG SPM100-11 (trade name, manufactured by Kimoto Co., Ltd.) of COLOR CONTROL SYSTEM. Test specimens are measured after white calibration. Further, the light reflectance of the blackened layer (also simply referred to as reflectance) is preferably 20% or less.

(Metal thin film layer formed by vapor deposition)
The metal thin film layer formed by vapor deposition is a layer provided as necessary in order to improve the adhesiveness of the bonding interface of the metal layer on the transparent resin substrate side. The vapor phase film formation for forming a metal thin film layer is a technique for forming a film by gasifying and depositing a metal on a deposition surface, and examples thereof include a sputtering method and a vapor deposition method. The material of the metal thin film formed by vapor phase deposition is not particularly limited, such as a single metal, an alloy, or a metal oxide. What is necessary is just to select suitably.
The metal thin film layer 14 may be the only layer interposed between the transparent resin base material and the metal plating layer as shown in FIG. 2, or the transparent resin base material 11 as shown in FIG. When other layers such as the blackening layer 13 are formed on the transparent resin base material side of the metal plating layer, the metal plating layer 15 is interposed between the other layer and the metal plating layer 15. It may improve the adhesion at the interface. Further, two or more metal thin film layers formed by vapor deposition may be provided. For example, although not shown, an alloy sputter layer is provided as a first metal thin film layer formed by vapor deposition on a transparent resin substrate, and formed by vapor deposition on the alloy sputtering layer. In addition, a copper sputter layer may be provided as the second metal thin film layer, and a copper plating layer as a metal plating layer may be further provided thereon.

  In the present invention, the metal thin film layer formed by vapor deposition is one having high conductivity and excellent adhesion to the blackened layer and the metal layer (however, in the case of the layer configuration as shown in FIG. 4C). Is preferably one having excellent adhesion to the transparent substrate 11 and the underlayer 18. Specifically, copper is preferably used, and a copper thin film is preferably formed by sputtering from the viewpoint of adhesion. As a target of the copper sputter layer 14, it is preferable to use copper having a purity of 99.99% by weight or more. The copper sputter layer 14 is an example of a metal thin film layer formed by vapor deposition. The thickness of the copper sputter layer 14 is not particularly limited, but is preferably 0.05 μm or more and 2 μm or less, more preferably 0.05 μm or more and 0.2 μm or less.

(Rust prevention layer)
As the conductive mesh layer 16, other layers may be appropriately formed or processed as necessary. For example, when the durability against rust is insufficient, a rust prevention layer may be provided. As in the case of the blackening layer described above, the rust preventive layer is regarded as a constituent layer included in the conductive mesh layer in the present invention as long as it maintains the mesh shape that is a shape characteristic of the mesh layer.

  The rust preventive layer is not particularly limited as long as it is less likely to rust than the conductive mesh layer covered with it, such as an inorganic material such as metal, an organic material such as resin, or a combination thereof. In some cases, the blackened layer is also covered with a rust-preventing layer, so that the particles of the blackened layer can be prevented from falling off and deformed, and the blackness of the blackened layer can be increased. Therefore, in the present invention, it is preferable to provide a rust-preventing layer on the blackened layer from the viewpoint of preventing the blackened layer from dropping or preventing alteration.

A conventionally well-known thing should just be employ | adopted for a rust prevention layer suitably, for example, is a metal thru | or alloys, such as chromium, zinc, nickel, tin, copper, or the layer of a metal compound of a metal oxide. These can be formed by a known plating method or the like. Here, if an example of a preferable antirust layer is shown by points, such as a rust prevention effect and adhesiveness, the chromium compound layer obtained by carrying out a chromate process after galvanizing will be mentioned. In addition, the rust preventive layer may contain a silicon compound such as a silane coupling agent in order to improve acid resistance during etching or acid cleaning.
In addition, the thickness of a rust prevention layer is about 0.07 micrometer-20 micrometers normally.

(Mesh shape)
FIG. 5 is a perspective view of an example of the electromagnetic wave shielding sheet used in the present invention. The conductive mesh layer 16 forming the mesh region 101 has a mesh shape in which the openings 103 are densely arranged. The mesh region has a first line portion 104A that forms a frame with the opening 103 and the first line portions 104A. It is comprised from the two line part 104B.
The shape of the mesh is arbitrary and not particularly limited, but a square is typical as the shape of the opening. Examples of the shape of the opening include a triangle such as a regular triangle, a square such as a square, a rectangle, a rhombus, and a trapezoid, a polygon such as a hexagon, a circle, and an ellipse.

The mesh region 101 has a plurality of openings 103 having these shapes, and the openings 103 are generally uniform in width and intersect with each other from the line-shaped first line portion 104A and the second line portion 104B. Become. Normally, the opening 103, the first line portion 104A, and the second line portion 104B have the same shape and the same size on the entire surface. To illustrate the specific size, the width W1 of the first line portion 104A between the openings 103 is preferably 25 μm or less, more preferably 20 μm, as shown in FIG. 5 in terms of the aperture ratio and the invisibility of the mesh. It is as follows. Further, it is preferable to secure a line width W1 of at least 5 μm or more in order to exhibit the electromagnetic wave shielding effect and prevent breakage. Further, the width W2 of the second line portion 104B is preferably 25 μm or less, and more preferably 20 μm or less. Moreover, it is preferable to secure line widths W1 and W2 of at least 5 μm or more for the expression of the electromagnetic wave shielding effect and prevention of breakage.
Also, the first width of the opening 103 is represented by (line pitch P1) − (line width W1), and in the present invention, it is preferably 150 μm or more, and 200 μm or more is the light transmission property and the optical described later. It is preferable from the point that air bubbles hardly remain in the opening during lamination with the filter. However, in order to express the electromagnetic wave shielding property in the MHz band, the maximum is 3000 μm or less. Furthermore, the second frontage width of the opening 103 is also expressed by (line pitch P2) − (line width W2), and is preferably 150 μm or more, more preferably 200 μm or more for the same reason as the first opening width. The maximum is 3000 μm or less.

In the present invention, the total thickness H of the line portions 104A and 104B in the finally obtained mesh region 101 is preferably 10 μm or less, more preferably 5 μm or less, and 3 μm or less. Is particularly preferred.
Note that the height H of the line portions 104A and 104B of the mesh region 101 refers to the total thickness including all the thicknesses of the layers forming the line portions. For example, when the line portions 104A and 104B are composed of the blackened layer 13, the copper sputtered layer 14, and the copper plated layer 15, as shown in FIG. Moreover, although not shown in figure, when a rust prevention layer and a 2nd blackening layer are formed on a copper plating layer, the thickness including a rust prevention layer and a 2nd blackening layer becomes a total thickness.
If the total thickness of the line portions 104A and 104B is too large, the level difference between the line portions 104A and 104B and the opening 103 becomes large when processed into a mesh, and bubbles tend to remain when the adhesive layer is laminated. Further, when the thickness of the line portions 104A and 104B is further increased, it becomes difficult to obtain a desired high-definition mesh shape by side etching or the like during etching.
On the other hand, when the total thickness H of the line portions 104A and 104B including the copper plating layer 15 is 10 μm or less, it is possible to save the amount of copper used and flatten the mesh surface. In particular, when the total thickness of the line portions 104A and 104B is 3 μm or less, the flattening effect is great.
On the other hand, if the total thickness H of the line portions 104A, 104B is too small, the thickness of the conductive mesh layer 16 is too small, and the electrical resistance value of the metal is increased and the electromagnetic wave shielding effect is easily impaired. In consideration of the electromagnetic shielding function, the thickness of the conductive mesh layer 16 including the copper plating layer 15 is preferably 1 μm or more, and more preferably 2 μm or more in the case of the above line width and line pitch. Is preferred. Therefore, the height H of the line part of the mesh region is preferably 1 μm or more, and more preferably 2 μm or more. In addition, the bias angle of the mesh region 101 (the angle formed between the line portion of the mesh and the outer periphery of the electromagnetic wave shielding sheet 10) is an angle at which moire (interference fringes) is difficult to occur in consideration of the pixel pitch of the display and the light emission characteristics. May be set as appropriate.

(Adhesive layer)
Although not illustrated in the electromagnetic wave shielding sheet of FIGS. 1 to 2, an adhesive layer (or a pressure-sensitive adhesive layer) may be used to bond the transparent resin base material and the conductive mesh layer. The adhesive layer is not particularly limited as long as it is a layer capable of bonding the conductive mesh layer and the transparent resin base material. In the present invention, the conductive mesh layer is configured as described above. When the metal foil and the transparent resin base material to be bonded are bonded to each other through the adhesive layer, and then the metal foil is meshed by etching, the adhesive layer preferably has etching resistance. Specifically, polyurethane resins such as polyester urethane, acrylic urethane, polyether urethane, acrylic resin, polyester resin, polyvinyl alcohol alone or a partially saponified product thereof, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer , Polyimide resin, epoxy resin and the like. Further, the adhesive layer (or pressure-sensitive adhesive layer) used for the adhesion may be an ultraviolet curable type or a thermosetting type. In particular, a polyurethane resin, an acrylic resin, or a polyester resin is preferable from the viewpoints of adhesion to a transparent resin base material, compatibility with a neon light absorber, dispersibility, and the like.
One or more neon light absorbers and / or color correction dyes may be contained in the adhesive layer.

  A metal foil for forming the transparent resin base material and the conductive mesh layer can be bonded via the adhesive layer by a dry lamination method or the like. Moreover, it is preferable that the film thickness of this adhesive bond layer is in the range of 0.5 μm to 50 μm, especially 1 μm to 20 μm. Thereby, the transparent resin base material and the conductive mesh layer can be firmly bonded, and the transparent resin base material is affected by an etching solution such as iron chloride at the time of etching to form the conductive mesh layer. This is because it can be prevented.

(Method for producing electromagnetic wave shielding sheet)
FIG. 6 is a flow sheet showing an example of a method for producing the electromagnetic wave shielding sheet 10 according to the present invention. A blackened layer forming step 90 for forming a blackened layer on the transparent resin substrate 11 such as a PET film is performed, and then a copper sputtered layer forming step 91 for depositing copper by a sputtering method is performed. Thereafter, a copper plating layer forming step 92 is performed. By adjusting the crystal orientation of the copper crystal during the copper plating layer forming step 92, the hardness and elongation of the copper layer are increased, so that the copper layer can be made thinner. Further, a second blackening layer forming step 95 for further forming a second blackening layer 80 on the copper plating layer is performed for the purpose of further improving image contrast by suppressing irregular reflection and back surface reflection of the PDP panel light. May be omitted. Also, the copper sputter layer forming step 91 can be omitted. Finally, the electromagnetic wave shielding sheet 10 is obtained by forming an opening having a desired shape in the patterning step 93.

In the blackening layer forming step 90, the transparent resin base material 11 is placed in the chamber of the sputtering apparatus, and the Ni—Cu alloy as a target is set in the chamber. Then, evacuation is started, and when the pressure becomes 1 × 10 ⁻⁴ Pa or less, an argon-oxygen mixed gas (for example, a purity of 99.8% or more is preferable) is supplied into the chamber. The ratio of argon: oxygen is preferably 95%: 5% to 30%: 70%, more preferably 90%: 10% to 70%: 30% (all are molar ratios). The supply amount of the mixed gas is determined in consideration of the size of the chamber, the performance of the vacuum apparatus, the required oxygen atmosphere, and the like.
The pressure in the chamber at the time of sputtering greatly affects the uniformity of the blackened layer 13, the stacking speed, and the amount of oxygen contained in the (Ni—Cu—O) compound. In the present invention, it is preferably 0.05 Pa or more and 0.5 Pa or less. By selecting the experimental conditions, a compound that has sufficient blackness as the blackening layer 13 and can absorb external light and suppress external light reflection (glare feeling) is formed. Furthermore, a (Ni—Cu—O) compound having excellent adhesion between the transparent resin substrate 11 and the copper sputter layer 14 and good etching properties can be obtained. Further, the blackening layer 13 according to the present invention has high adhesion to both the transparent resin base material 11 and the copper sputter layer 14, but particularly high adhesion to the copper sputter layer 14 has an action of shielding electromagnetic waves. This is advantageous from the viewpoint of effective expression.

The composition ratio of the target Ni—Cu alloy is not particularly limited. However, it is preferable to use Ni: Cu = 80 wt%: 20 wt% to 65 wt%: 35 wt%, and the purity is preferably 99.99 wt% or more. Moreover, the composition ratio of Ni and Cu in the (Ni—Cu—O) compound can be determined by appropriately selecting the composition ratio of the target Ni—Cu alloy. Moreover, the oxygen content in the (Ni—Cu—O) compound can be adjusted by adjusting the supply amount of the oxygen gas.
The target is not limited to a Ni—Cu alloy, but is Ni—Cu—X, where X is one or more elements, for example, a ternary alloy, a quaternary alloy, Ni, etc. A multi-element material containing Cu and Cu may be used.

  When the blackening layer 13 according to the present invention is formed, the oxygen content of the (Ni—Cu—O) compound forming the blackening layer 13 is improved by increasing the oxygen supply amount in the chamber. When it is a normal compound, the reflectance decreases and the blackness increases when the oxygen content increases, but the adhesion with the transparent resin substrate or the metal plating layer deteriorates, and the conductivity deteriorates as another problem. Therefore, the electromagnetic wave shielding property tends to deteriorate. However, the (Ni—Cu—O) compound that forms the blackening layer 13 according to the present invention has sufficient adhesion with an adjacent layer even when the amount of oxygen that sufficiently increases the blackness is included. In addition, it is difficult for the conductivity to decrease.

  The (Ni—Cu—O) compound, which is a component of the blackening layer 13 according to the present invention, also has an advantage of being excellent in etching property when performing the photolithography method in the patterning step 93. At the time of etching, it is necessary that a portion desired to remain as a mesh pattern is coated with a resist material to be protected from the corrosive liquid, and only a portion to be removed is dissolved in the corrosive liquid. Since the (Ni—Cu—O) compound according to the present invention is easily dissolved in a corrosive liquid such as ferric chloride and ammonium cerium nitrate, it has excellent etching properties. In addition, in the manufacturing method of the electromagnetic wave shielding sheet 10 according to the present invention, a manufacturing intermediate may be immersed in an alkaline solution in a photolithography process. Therefore, the manufacturing intermediate may use an alkaline solution when removing the resist. Therefore, in some cases, it is necessary to have alkali resistance, but the (Ni—Cu—O) compound forming the blackening layer 13 according to the present invention is also excellent in alkali resistance.

  A copper sputter layer forming step 91 for forming the copper sputter layer 14 is performed on the upper surface of the blackening layer 13, but the copper sputter step 91 may be omitted. The copper sputter layer 14 uses copper as a target, and applies a high voltage (for example, 0.3 kV to 0.6 kV; 2 kW to 10 kW) to the argon-oxygen gas to ionize argon. By applying this ionized argon to the target copper, copper ions jump out of the target onto the transparent resin substrate 11, and a copper layer (copper sputter) is formed on the surface of the blackened layer 13 on the transparent resin substrate 11. Layer) 14.

In order to laminate the copper plating layer 15, an electrolytic plating method, an electroless plating method, and the like can be mentioned, but it is preferable to perform the electrolytic plating method from the viewpoint of production speed. It is considered that the copper plating layer 15 formed on the transparent resin base material 11 is deposited as the copper crystal grows upward from the base surface.
The copper crystal has a face-centered cubic lattice, and when the crystal plane is represented by a plane index, at least three crystals, that is, a crystal plane represented by a plane index (111) with respect to the crystal axis of the face-centered cubic lattice. There may be a crystal having, a crystal having a crystal plane represented by a plane index (200), and a crystal having a crystal plane represented by a plane index (220).
Here, the plane index of the crystal plane is a means for expressing the direction of the crystal plane with respect to the crystal axis. The length by which the crystal plane cuts the crystal axis is expressed as a unit of lattice constant, and the reciprocal of the expressed length is obtained. The reciprocal ratio is reduced to three integers (usually the smallest integer combination) that make up the same ratio. The reduced integer is enclosed in parentheses and determined as the plane index of the crystal plane.

Accordingly, in the copper plating layer 15, crystals grown with the (111) surface facing upward (in a state parallel to the surface of the plating layer), the (200) surface facing upward (the surface of the plating layer) There may be a crystal grown in a state parallel to the surface and a crystal grown in a state where the (220) plane faces upward (in a state parallel to the surface of the plating layer).
The ratio of the number of crystal planes parallel to the surface of the copper plating layer 15 is the ratio of the number of unit lattices of crystals in which the same crystal plane faces the deposition direction of the plating. It is also the ratio of the number of unit lattices of crystals whose crystal growth directions are the same in relation to the axis, and is a means for indicating the orientation state of the copper crystals constituting the copper plating layer 15.

  In the present invention, the crystal orientation of copper constituting the copper plating layer 15 is adjusted so that the copper plating layer 15 formed on the transparent resin base material 11 is not damaged during the processing of the electromagnetic wave shielding sheet 10. The hardness and elongation rate of the copper plating layer 15 are improved. Specifically, the ratio of the number of crystal planes parallel to the surface of the copper plating layer 15 is the plane index peak ratio of the crystal plane specified by XRD measurement in which the surface of the copper plating layer 15 is irradiated with X-rays. When expressed, the crystal orientation of copper is adjusted so that the ratio of the (200) plane or (220) plane strength to the (111) plane strength is 50% or more. Alternatively, the crystal orientation of copper is adjusted so that the ratio of the total strength of the (200) plane and the (220) plane to the (111) plane strength is 70% or more.

Here, the XRD measurement refers to a crystal analysis method based on X-ray diffraction (X-Ray Diffraction) measurement. X-rays are incident on the crystal to be measured, and the intensity of Bragg reflection on each crystal plane such as the (111) plane in the crystal is measured. From this, the abundance ratio of each crystal plane is obtained from the type of crystal plane present in the crystal and its intensity ratio. As a specific measurement method, a known method or apparatus already established in the field of crystal lattice analysis may be used.
The peak ratio of crystal planes identified by such XRD measurement is a crystal lattice having a specific crystal growth direction in relation to the ratio of the number of crystal planes facing a specific direction or the crystal axis in a polycrystalline system. The abundance ratio of.

  In this way, the ratio of the number of crystal planes having a specific orientation existing in a region having a certain extent in the plane direction, that is, the ratio of crystal orientation of each single crystal particle constituting the polycrystal (distribution). ) Can be measured.

According to JCPDS (Joint Committee on Powder Diffraction standards), which is standard data for powder X-ray diffraction, the standard XRD peak ratio (peak ratio of random orientation) of copper crystals is (111) plane: (200) Plane: (220) plane = 100: 46: 20. In this case, the (111) plane has the largest peak. This state is called (111) orientation. Since the (200) plane strength is 46% with respect to the (111) plane strength of 100% and does not reach 50%, the crystal orientation of copper is adjusted to 50% or more by the first plating method described later. To do.
Regarding the relationship between the (111) plane strength and the (220) plane strength, the (220) plane strength is only 20% with respect to the (111) plane strength of 100%, and does not reach 50%. The crystal orientation of copper is adjusted to 50% or more by the method.
In the relationship between the (111) plane strength and the total strength of the (200) plane and the (220) plane, the ratio of the total strength of the (200) plane and the (220) plane with respect to 100% of the (111) plane strength is 46. % + 20% = 66%, and since it has not reached 70%, the crystal orientation of copper is adjusted to 70% or more by the third plating method described later.

  As a copper plating solution by the electrolytic plating method, a known plating bath such as a copper sulfate bath, a copper bromide bath, a copper borofluoride bath, a copper pyrophosphate bath can be used, but a copper sulfate bath is a typical plating bath. Used. As the composition of the copper sulfate bath, for example, a copper sulfate and an aqueous solution containing sulfuric acid and a plating additive for adjusting the orientation of copper crystals are used. The sulfuric acid concentration is about 150 to 220 g / L (liter), and the copper sulfate concentration is about 50 to 85 g / L for pentahydrate. Hereinafter, first to third plating methods will be particularly described as preferable methods for adjusting the crystal orientation of the copper plating layer 15.

In the first to third plating methods, examples of the orientation control component contained in the plating additive include hydrocarbon polymer compounds, sulfur-containing hydrocarbon compounds, proteins, glue, amines, alkaloids, mercaptans, Known compounds such as sulfide or various dye-based compounds can be used. One or more of these orientation adjusting components are appropriately selected and used. The addition amount is about 1 to 100 g / L. Further, if necessary, hydrochloric acid may be added at a chlorine concentration of about 40 to 80 mg / L in order to roughen the surface of the copper plating layer 15. The plating conditions may be general settings. For example, the bath temperature is 20 to 30 ° C., the current density is 1 to 3 A / dm ² , the plating time is 30 minutes to 2 hours, and the plating bath is stirred. After the plating layer is deposited, it is preferable to perform an annealing treatment as necessary in order to stabilize the crystal orientation. The annealing conditions are, for example, 100 to 200 ° C., 30 minutes to 2 hours.
It is known that the parallel alignment of the copper crystal (200) plane and the (220) plane on the surface of the copper plating layer depends on the blending ratio of the constituent components of the additive. In order to increase the ratio of the crystal planes parallel to the surface of the copper plating layer being the (200) plane and the (220) plane, the blending ratio of the components of the plating additive may be adjusted.

In the first plating method, the ratio of the crystal plane parallel to the surface of the copper plating layer 15 is the (200) plane is increased, and particularly as an example of a preferable additive for 50% or more, for example, hydrocarbon And the like, and the (200) plane strength of the copper crystal is the standard strength value (46%). ), That is, a state preferentially oriented in the (200) plane. The degree of the preferential orientation is adjusted so that the ratio of the (200) plane strength to the (111) plane strength is 50% or more.
In the second plating method, the ratio of the crystal plane parallel to the surface of the copper plating layer 15 is the (220) plane is increased. Examples thereof include a compound containing a molecular compound as a main component and not containing a sulfur-containing hydrocarbon compound. In particular, a blend composed only of a hydrocarbon-based polymer compound is particularly preferable, whereby the (220) plane strength of the copper crystal is higher than the standard strength value (20%), that is, priority is given to the (220) plane. It will be in the state where it is oriented. The degree of the preferential orientation is adjusted so that the ratio of the (220) plane strength to the (111) plane strength is 50% or more.

  In the first or second plating method, the (200) plane strength or (220) plane strength of the copper crystal in the copper plating layer 15 is preferentially oriented so as to be 50% or more with respect to the (111) plane strength. As long as it is, (200) plane orientation (state where the orientation plane with the highest strength is the (200) plane) or (220) plane orientation (state where the orientation plane with the highest strength is the (220) plane) The effect can be obtained even if it is not, but the (200) plane orientation or (220) plane orientation is more preferable because the copper plating layer 15 can obtain higher hardness or elongation.

In the third plating method, the ratio of the crystal plane parallel to the surface of the copper plating layer 15 being the (200) plane or the (220) plane is increased, and in particular, the total strength is preferably 70% or more. As an example of an additive, the mixing | blending which has a hydrocarbon type polymer compound as a main component and does not contain a sulfur-containing hydrocarbon compound is mentioned. In particular, a blend composed only of a hydrocarbon-based polymer compound is particularly preferred, whereby the total strength of the (200) plane and (220) plane of the copper crystal is greater than the standard strength value (66%). Specifically, the total strength is adjusted to be 70% or more.
If the total strength of the (200) plane and the (220) plane of the copper crystal in the copper plating layer 15 reaches 70% or more with respect to the (111) plane strength, the hardness and elongation of the copper plating layer 15 From the viewpoint of obtaining a more excellent effect, the total strength of the (200) plane and the (220) plane is preferably 100% or more with respect to the (111) plane strength. Moreover, as a result of which one of the (200) plane and the (220) plane is larger than the standard strength (46% for the (200) plane and 20% for the (220) plane), these two A sufficient effect can be obtained if the total strength of the crystal planes reaches 70% or more, but from the viewpoint of obtaining a more excellent effect, it is preferable that at least the (200) plane strength is greater than 46%. Furthermore, it is particularly preferable that the (200) plane strength is greater than 46% and the (220) plane strength is greater than 20%.

Although the first to third plating methods have been described as methods for improving the hardness and elongation rate of the copper plating layer 15, the present invention is not limited to these methods. As the hardness of the copper plating layer 15 is improved, the copper plating layer 15 is particularly resistant to rubbing during the processing process, and scratch resistance is improved. Further, by improving the elongation rate of the copper plating layer 15, it becomes particularly resistant to tension during the processing process, and crack resistance is improved. And by improving both the flaw resistance and crack resistance of the copper plating layer 15, it becomes difficult to damage the copper plating layer 15 during the manufacturing process of the electromagnetic wave shielding sheet, and it can be expected to improve the throughput.
Therefore, it is possible to facilitate surface flattening by forming a thin copper plating layer to save the amount of copper used and reducing the uneven step of the mesh pattern.
The above-described improvement in hardness and elongation of the copper plating layer 15 can be known by the following measurement method of Vickers hardness and elongation.
The Vickers hardness can be measured using a general Vickers hardness measuring device (for example, model name MVK-G2 manufactured by AKASHI Co., LTD) with an indenter load of 10 g and a holding time of 15 seconds.

  Further, the elongation can be performed in accordance with JIS Z-2241 (1980) “Metal Material Tensile Test Method”, and using a general tensile test apparatus (for example, manufactured by SHIMADZU Co., LTD) It can be measured with a thickness of 18 μm × width of 10 mm × length of 50 mm and a tensile speed of 10 mm / min.

  In order to further increase the blackness of the electromagnetic wave shielding sheet 10 on the copper plating layer 15, a second blackening layer 80 may be further formed (see FIG. 4A). When forming the second blackened layer 80, a second blackened layer forming step 95 is performed after the copper plating layer forming step 92, and a patterning step 93 is performed after the second blackened layer forming step 95. In addition, the material of the blackening layer 13 mentioned above can be applied for a raw material, a formation method, etc. The second blackened layer 80 is also formed using a Ni—Cu—O-based compound by the same sputtering method as the blackened layer 13. The experimental conditions are almost the same as the previous blackening layer 13, but note that the crystal orientation of the copper crystal of the copper plating layer 15 does not break the relationship between the (111) plane, the (200) plane, and the (220) plane. I need to pay.

The transparent resin base material 11 on which the copper plating layer 15 is formed is placed in a chamber of a sputtering apparatus, and a Ni—Cu alloy as a target is set in the chamber. Then, evacuation is started, and when the pressure becomes 1 × 10 ⁻⁴ Pa or less, an argon-oxygen mixed gas is supplied into the chamber. Each experimental condition such as the ratio of argon: oxygen, chamber size, mixed gas supply amount, and the like is the same as the method for forming the blackened layer 13 described above. The thickness of the second blackening layer 80 is not particularly limited, but is preferably from 80 mm (= 8 nm) to 300 mm (= 30 nm), more preferably from 120 mm to 160 mm. The black density of the second blackened layer 80 is preferably 0.6 or more, the light reflectance of the second blackened layer 80 is preferably 20% or less, and the Y value of reflection is preferably 20 or less. For these measurements, those described in the formation of the blackening layer 13 can be applied.

In the present invention, a known blackening layer 81 is formed on the uppermost surface of the conductive mesh layer 16 such as the upper surface of the copper plating layer 15 or the upper surface of the second blackening layer 80, and the known blackening layer 81 is included. A conductive mesh layer can also be used.
The known blackening layer 81 shown in FIG. 4B is formed by roughening the surface of the copper plating layer 15, applying a light absorbing material over the entire visible light spectrum (blackening), or using both in combination. This can be done by either When roughening the copper plating layer 15 to form the known blackening layer 81, the cathode is subjected to cathodic electrolysis in an electrolytic solution composed of sulfuric acid, copper sulfate, cobalt sulfate, etc., and the cationic particles are adhered. Cathodic electrodeposition that can be used. By providing cationic particles, the particles become rougher and at the same time black is obtained. As the cationic particles, copper particles and alloy particles of copper and other metals can be applied, but copper-cobalt alloy particles are preferable. The average particle size of the cationic particles is preferably about 0.1 μm to 1 μm from the viewpoint of black density. In addition, as the blackening layer forming method, nickel-zinc alloy, nickel sulfide, or blackening nickel plating made of a composite of these, and copper oxide can also be suitably used.

A conductor layer including a blackened layer is formed through the above-described steps. The conductor layer may be patterned after sequentially forming all the layers constituting the conductor layer, or may be patterned at the stage of forming a part of the conductor layer or during the formation.
As one method of the patterning process 93, the following three methods are mentioned, for example.
(1) A method of printing conductive ink in a pattern on a transparent substrate. As the conductive ink, a composition in which conductive particles such as silver and graphite are dispersed in a resin binder such as an acrylic resin and a polyester resin is used. As a printing method, methods such as silk screen, intaglio and flexo can be applied. When the conductivity is insufficient only with the conductive ink, there is also a method of plating a metal layer such as copper or silver on the conductive ink layer (see, for example, JP-A-2000-13088).
(2) Apply a conductive ink or a photosensitive coating solution containing a chemical plating catalyst to the entire surface of the transparent substrate to form a coating layer. After forming the coating layer into a mesh by photolithography, copper is applied onto the mesh. Method of plating (for example, Sumitomo Osaka Cement Co., Ltd., New Materials Division, New Materials Research Institute, New Materials Research Group, “Photoresolvable Chemical Plating Catalyst”, [online], date not listed, Sumitomo Osaka Cement Co., Ltd. [Search January 7, 2003], Internet <URL: http://www.socib.com/product/hproduct/display.html>).
(3) A metal thin film is formed on one surface of the transparent substrate by sputtering or the like to form a conductive treatment layer, and a copper plating layer is formed thereon by electrolytic plating. Forming a transparent layer or other known blackening layer to prepare a transparent substrate that has completed the formation of all the layers of the conductor layer, and the conductor layer on the transparent substrate is prepared by a photolithography method. The mesh shape is used (see, for example, Japanese Patent No. 3502979 and Japanese Patent Application Laid-Open No. 2004-241761).
(4) A metal foil is bonded to one surface of a transparent substrate by a dry lamination method to form a conductor layer, and the conductor layer on the transparent substrate is meshed by a photolithography method (for example, patent No. 3388682).

  Among them, in the present invention, in particular, a process for preventing the blackened layer from adhering to the opening is unnecessary, and since the transparency and mesh accuracy are excellent, the display image can be satisfactorily viewed, and the existing equipment is used. From the point that many of them can be continuously performed in the manufacturing process, there is little warping or mixing of air bubbles, etc., and the yield is good, the yield is low, and the quality is good in a short process (high production efficiency). It is particularly preferable to use the method 3). A method for forming the conductor layer by the method (3) will be described in detail.

  The patterning process 93 which makes the conductor layer 16 on the transparent resin substrate 11 provided as described above into a mesh shape by photolithography will be described. After providing a resist layer on the surface of the conductor layer 16 on the transparent resin substrate 11 prepared as described above, forming a mesh pattern, and removing the portion of the conductor layer 16 not covered with the resist layer by etching, The resist layer is removed to form a mesh-like conductor layer 16.

The surface on the conductor layer 16 side of the transparent resin base material 11 is made into a mesh shape by a photolithography method, and the mesh-like region 101 is formed. This patterning step 93 is also a roll-shaped laminated body (transparent resin base material 11 and conductor layer 16 that is continuously wound in a band shape. In the following description, at least one layer is formed on the transparent resin base material. (Referred to as a laminated body) is preferably processed (winding processing, roll-to-roll processing). While the laminate is conveyed continuously or intermittently, masking, etching, and resist peeling are performed in a stretched state without looseness.
Next, for masking, for example, a photosensitive resist is applied onto a conductor layer forming a mesh-like region, dried, and then closely exposed with a photomask having a predetermined pattern, water-developed, and hardened. Etc. and baking. Note that either a negative type or a positive type of photosensitive resist can be used. When the photosensitive resist is a negative type, the first line portion and the second line portion (conductor layer) of the mesh pattern of the photomask are transparent. When the photosensitive resist is a positive type, the mesh pattern of the photomask has a transparent opening. Moreover, as an exposure pattern, it is a desired pattern as an electromagnetic wave shielding sheet, and is composed of a pattern of a mesh area at a minimum. Further, if necessary, a grounding area pattern is added to the outer periphery of the mesh area.
In the winding process, resists such as casein, PVA, and gelatin are dipped (dipped) on the surface of the conductor layer forming the mesh-like region while being transported continuously or intermittently in the winding process, curtain coating , Do it by a method such as pouring. Moreover, a dry film resist may be used instead of application | coating, and workability | operativity can be improved. In the case of a casein resist (a kind of milk protein), baking is performed at 200 to 300 ° C., but in order to prevent warping of the transparent resin substrate, a low temperature is preferable.

  Etching is performed after masking and exposure. As an etchant used for etching, an aqueous solution of ferric chloride or cupric chloride that can be easily circulated is preferable in the present invention in which etching is continuously performed. Etching is basically the same process as a facility for manufacturing a shadow mask for a color TV cathode ray tube that etches a strip-like continuous steel material, particularly a thin plate having a thickness of 20 μm to 80 μm. That is, existing manufacturing equipment for shadow masks can be diverted, and from masking to etching can be produced consistently and continuously, which is extremely efficient. After etching, the substrate may be dried after washing with water, stripping the resist with an alkaline solution, and washing. Since the transparent resin base material is exposed on the surface of the mesh opening formed in this way, the transparency of the mesh opening is good. By the above mesh processing, the conductor layer 16 becomes a mesh shape, and the electromagnetic wave shielding sheet 10 is obtained.

  The electromagnetic wave shielding sheet 10 according to the present invention preferably has various optical filter functions in the pressure-sensitive adhesive layer 20, but an optical filter is further laminated and bonded to the side having the mesh-like conductor layer 16. Also good. As an optical filter, on the transparent resin substrate of the optical filter, various function expressing layers such as a near infrared absorbing layer, a neon light absorbing layer, an ultraviolet absorbing layer, an antireflection layer, a hard coat layer, an antiglare layer, an antifouling layer. A layer in which one or two or more layers are laminated is used.

(Modification of manufacturing method of electromagnetic wave shielding sheet)
FIG. 7 is a flow sheet showing another example of the method for producing an electromagnetic wave shielding sheet according to the present invention, and FIG. 4C shows a layer structure of a mesh-like conductor layer formed according to the flow sheet shown in FIG. It is sectional drawing which showed the example typically. The mesh-shaped conductor layer 16D of FIG. 4C is a transparent resin base material in the order of an underlayer (usually a Ni—Cr alloy layer) 18, a copper sputter layer 14, a copper plating layer 15, and a blackening layer 13 according to the present invention. 11 is the same as the conductive mesh layer 16 shown in FIG. 3 and FIG.

  After forming the underlayer 18 in the underlayer forming step 110 as necessary on the transparent resin substrate 11 such as a PET film, a copper sputter layer forming step 111 for depositing copper by a sputtering method is performed, and the copper sputter layer 14 After forming, a copper plating layer forming step 112 is performed. In order to increase the hardness and elongation of the copper layer by adjusting the crystal orientation ((110) plane, (200) plane, (220) plane) of the copper crystal during the copper plating layer forming step 112 As in the case of the conductor layer 16, the copper layer can be made thin. Then, a blackened layer forming step 113 for forming the blackened layer 13 on the copper plating layer 15 is performed. Finally, the electromagnetic wave shielding sheet 115 is obtained by forming an opening having a desired shape in the patterning step 114.

Conductive treatment is performed prior to sputtering or metal electroplating, and a base layer forming step 110 for forming the base layer 18 shown in FIG. 4C is performed.
As a method for forming the underlayer 18, a thin film made of a known conductive material may be formed. Examples of the conductive material include metals such as gold, silver, platinum, copper, aluminum, tin, iron, nickel, and chromium, or alloys of these metals (for example, nickel-chromium alloy). Moreover, transparent metal oxides, such as a tin oxide, ITO, and ATO, may be sufficient. The conductive treatment may be a single layer or multiple layers (for example, a laminate of a nickel-chromium alloy and a copper layer). The underlayer is used. The thickness of the underlayer is preferably an extremely thin layer of about 0.001 to 1 μm, as long as necessary conductivity can be obtained at the time of plating.

  Then, a copper sputter layer 14 is formed in a copper sputter layer forming step 111. Alternatively, the formation of the copper sputter layer 14 may be omitted, and the copper plating layer 15 may be formed directly on the base layer 18 by an electrolytic plating method. The copper sputter layer 14 can be performed under the conditions described above (see the copper sputter layer forming step 91). The copper plating layer forming step 112 by the electrolytic plating method for laminating the copper plating layer 15 is the same as the above-described condition (see the copper plating layer forming step 92), and copper plating such as the electrolytic plating method is performed. A copper plating layer 15 is formed. The copper plating layer 15 can be performed under the conditions described above. The degree of orientation of the copper crystal (111), (200), and (220) are adjusted in the same manner as in the conductor layer 16.

The blackened layer 13 is formed in the blackened layer forming step 113 under substantially the same conditions as the second blackened layer 80 in the conductor layer 16B (see FIG. 4A) (see the second blackened layer forming step 95). The transparent resin base material 11 on which the copper plating layer 15 is formed is placed in a chamber of a sputtering apparatus, and a Ni—Cu alloy as a target is set in the chamber. Then, evacuation is started, and when the pressure becomes 1 × 10 ⁻⁴ Pa or less, an argon-oxygen mixed gas is supplied into the chamber. The experimental conditions such as the ratio of argon: oxygen, chamber size, and mixed gas supply amount are the same as the method for forming the second blackening layer 80 described above.
As a result, the blackened layer 13 is formed on the uppermost surface of the conductor layer 16D as shown in FIG. 4C. The thickness of the blackening layer 13 is not particularly limited, but 80 mm (= 8 nm) or more and 1000 mm (= 100 nm) or less is applicable, but 100 mm or more and 300 mm or less is preferable, and more preferably 120 mm or more and 160 mm or less. is there. The black density of the blackened layer 13 is preferably 0.6 or more, the light reflectance of the blackened layer 13 is preferably 20% or less, and the Y value of reflection is preferably 20 or less. For these measurements, those described in the formation of the second blackening layer 80 can be applied.

  Finally, a patterning step 114 is performed to form an opening. The patterning is preferably performed by the above-described photolithography method (see the patterning step 93). The corrosion solution (etching solution) is preferably an aqueous solution of ferric chloride or cupric chloride that easily dissolves the (Ni—Cu—O) compound.

2. Adhesive layer The adhesive layer according to the present invention has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co) , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br , Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / The composite tungsten oxide fine particles represented by y ≦ 1.1 and 2.2 ≦ z / y ≦ 3.0) and the pressure-sensitive adhesive may be contained, and further other components may be contained.
In the pressure-sensitive adhesive layer according to the present invention, composite tungsten oxide fine particles are dispersed in the pressure-sensitive adhesive layer, and the transparency required for the composite filter and the near infrared absorption function are ensured.

(1) Composite tungsten oxide fine particles The general formula MxWyOz (wherein M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, One or more elements selected from Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1 .1, 2.2 ≦ z / y ≦ 3.0) function as a near infrared absorber in the present invention. Therefore, the pressure-sensitive adhesive layer according to the present invention absorbs a near infrared region generated when the plasma display panel emits light using xenon gas discharge, that is, a wavelength region of 800 nm to 1,100 nm. The near infrared transmittance is preferably 20% or less, more preferably 15% or less.

  The composite tungsten oxide fine particles represented by the general formula MxWyOz is excellent in durability when it has a hexagonal, tetragonal or cubic crystal structure, and is therefore selected from the hexagonal, tetragonal and cubic crystals. Preferably it contains more than one crystal structure. For example, in the case of composite tungsten oxide fine particles having a hexagonal crystal structure, preferable M elements include Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Examples thereof include composite tungsten oxide fine particles containing one or more selected elements. Among them, the M element is preferably Cs (cesium) from the viewpoint of durability.

At this time, the addition amount x of M element to be added is preferably 0.001 or more and 1.0 or less, and more preferably around 0.33. This is because the value of x calculated theoretically from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. On the other hand, the abundance z of oxygen is preferably 2.2 or more and 3.0 or less. For example, Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like can be mentioned, provided that x and z fall within the above ranges. Useful near infrared absorption characteristics can be obtained.

Such composite tungsten oxide fine particles may be used alone or in combination.
In addition, coating the surface of the composite tungsten oxide fine particles with an oxide containing one or more elements of Si, Ti, Zr, and Al can further improve the weather resistance. preferable.

  Further, the average dispersed particle size of the composite tungsten oxide fine particles is preferably 800 nm or less, more preferably 200 nm or less, particularly preferably 100 nm or less, from the viewpoint of the transparency of the pressure-sensitive adhesive layer. Here, the average dispersed particle size refers to a volume average particle size, and can be measured using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device manufactured by Nikkiso Co., Ltd.).

  Although content of composite tungsten oxide microparticles | fine-particles is not specifically limited, It is preferable that it is 1-25 weight% in an adhesive layer. If the content is more than 1% by weight, a sufficient near-infrared absorbing function can be exhibited, and if it is 25% by weight or less, a sufficient amount of visible light can be transmitted.

(2) Adhesive The adhesive used in the present invention uniformly disperses the composite tungsten oxide fine particles and the like, imparts film-forming properties, and further functions as an application surface of the composite filter. The pressure-sensitive adhesive is not particularly limited as long as it achieves film formability, transparency, pressure-sensitive adhesiveness, and dispersibility of the composite tungsten oxide fine particles, and is appropriately selected depending on the layer configuration adjacent to the pressure-sensitive adhesive layer. Can be used. The higher the transparency as the pressure-sensitive adhesive layer is, the better. However, the light transmittance in the visible light region of 380 to 780 nm is preferably 70% or more, more preferably 80% or more. By optimizing the pressure-sensitive adhesive used and the thickness, the pressure-sensitive adhesive layer of the present invention also functions as an impact resistant layer.

The pressure-sensitive adhesive used in the present invention is preferably one that can favorably disperse the composite tungsten oxide fine particles.
Specifically, the composite tungsten oxide fine particles are dispersed in a resin to form a coating film having a film thickness of 25 μm, and when the haze value according to JIS K7136 is measured, the haze value is 15 or less. It is preferable that a resin is selected and used at a mixing ratio at which the haze value is 5 or less. The haze value is more preferably 3 or less, and particularly preferably 2 or less. In the case of using an additive for improving dispersion when dispersing the composite tungsten oxide fine particles, it is preferable that the resin and the additive are used in such a mixing ratio that the above haze value is obtained together with the additive. .

  As in the first embodiment (see FIG. 1), when the conductive mesh layer 16 is present on the pressure-sensitive adhesive layer 20 side in the electromagnetic wave shielding sheet 10, the pressure-sensitive adhesive layer is formed of the conductive mesh layer. It is provided on the conductive mesh layer so as to flatten the unevenness and expose a part of the peripheral edge of the conductive mesh layer, and also serves as a flattening layer of the conductive mesh layer.

  Here, the pressure-sensitive adhesive refers to one type of adhesive. Of the adhesives, the adhesive is bonded only by the pressure on the surface, only by pressing moderately, usually by light pressure. Say what you can. In order to develop the adhesive strength of the pressure-sensitive adhesive, usually, physical energy or action such as heating, humidification, radiation (ultraviolet ray, electron beam, etc.) irradiation is unnecessary, and chemical reaction such as polymerization reaction is also unnecessary. In addition, the pressure-sensitive adhesive can maintain the adhesive strength to the extent that it can be re-peeled after bonding. There is no restriction | limiting in particular as such an adhesive, It has moderate adhesiveness (adhesive force), transparency, and coating suitability from what is conventionally used as a well-known adhesive, The composite filter of this invention A transmission spectrum that does not substantially change the transmission spectrum is appropriately selected.

  Examples of the pressure-sensitive adhesive include natural rubber, synthetic rubber, acrylic resin (hereinafter also abbreviated as acrylic), polyvinyl ether, urethane resin, and silicone resin. Specific examples of synthetic rubbers include styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block. A copolymer is mentioned. Specific examples of the silicone resin system include dimethylpolysiloxane. These pressure-sensitive adhesives can be used alone or in combination of two or more.

  An acrylic adhesive is mentioned as an adhesive suitably used. The acrylic pressure-sensitive adhesive is a polymer containing at least a (meth) acrylic acid alkyl ester monomer. A copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group, or (meth) acrylic acid having an alkyl group having about 1 to 18 carbon atoms A copolymer using two or more kinds of alkyl ester monomers is generally used. In the present invention, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

  Examples of (meth) acrylic acid alkyl ester monomers used here include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, sec-propyl (meth) acrylate, N-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples thereof include n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, undecyl (meth) acrylate and lauryl (meth) acrylate. Moreover, it is preferable that the said (meth) acrylic-acid alkylester is copolymerized in the quantity of 30-99.5 weight part in the acrylic adhesive.

Moreover, as a monomer which has a carboxyl group which forms an acrylic adhesive, monomers containing a carboxyl group such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, monobutyl maleate and β-carboxyethyl acrylate are used. Can be mentioned.
Furthermore, in addition to the above, the acrylic pressure-sensitive adhesive used in the present invention may be copolymerized with a monomer having another functional group within a range that does not impair the characteristics of the acrylic pressure-sensitive adhesive. Examples of monomers having other functional groups include monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and allyl alcohol; (meth) acrylamide, N-methyl Monomers containing amide groups such as (meth) acrylamide and N-ethyl (meth) acrylamide; Monomers containing amide groups and methylol groups such as N-methylol (meth) acrylamide and dimethylol (meth) acrylamide; Monomers having functional groups such as monomers containing amino groups such as (meth) acrylate, dimethylaminoethyl (meth) acrylate and vinylpyridine; epoxy group-containing monomers such as allyl glycidyl ether and (meth) acrylic acid glycidyl ether It is below. In addition to these, fluorine-substituted (meth) acrylic acid alkyl ester, (meth) acrylonitrile, and the like, vinyl group-containing aromatic compounds such as styrene and methylstyrene, vinyl acetate, and vinyl halide compounds can be used.

Furthermore, in the acrylic pressure-sensitive adhesive used in the present invention, in addition to the monomer having other functional groups as described above, another monomer having an ethylenic double bond can be used. Examples of the monomer having an ethylenic double bond include diesters of α, β-unsaturated dibasic acids such as dibutyl maleate, dioctyl maleate and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate. Vinyl ether; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyl toluene; (meth) acrylonitrile and the like.
In addition to the monomer having an ethylenic double bond as described above, a compound having two or more ethylenic double bonds may be used in combination. Examples of such compounds include divinylbenzene, diallyl malate, diallyl phthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide, and the like.

  Furthermore, in addition to the above-described monomers, monomers having an alkoxyalkyl chain can be used. Examples of alkoxyalkyl esters of (meth) acrylic acid include 2-methoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, and 3-methoxypropyl (meth) acrylate. , 2-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate And so on.

  Moreover, the homopolymer of a (meth) acrylic-acid alkylester monomer may be sufficient. For example, (meth) acrylic acid ester homopolymers include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, poly (meth) Examples include octyl acrylate.

As a copolymer containing 2 or more types of acrylate units, methyl (meth) acrylate- (meth) ethyl acrylate copolymer, (meth) methyl acrylate- (meth) butyl acrylate copolymer, ( Examples include methyl (meth) acrylate- (meth) acrylic acid 2-hydroxyethyl copolymer, methyl (meth) acrylate- (meth) acrylic acid 2-hydroxy-3-phenyloxypropyl copolymer, and the like.
As a copolymer of (meth) acrylic acid ester and other functional monomers, (meth) methyl acrylate-styrene copolymer, (meth) methyl acrylate-ethylene copolymer, (meth) acrylic An acid methyl- (meth) acrylic acid 2-hydroxyethyl-styrene copolymer may be mentioned.

  As a commercial item of an acrylic adhesive, for example, trade name: TU-41A (manufactured by Yodogawa Paper Mill), trade name: No. 591, no. 5915, no. 5919M, CS9621, LA-50, LA-100, HJ-9210, No. 595B (manufactured by Nitto Denko Corporation), trade name: SK Dyne SK2094 (manufactured by Soken Chemical Co., Ltd.) and the like are preferably used from the viewpoint of low haze and adhesive strength.

(3) Neon light absorber The neon light absorption function is installed to absorb neon light emitted from the plasma display panel, that is, the emission spectrum of neon atoms. When a neon light absorber is included, at least orange light emission from the display can be suppressed, and a bright red color can be obtained. Since the emission spectrum band of neon light has a wavelength of 550 to 640 nm, the spectral transmittance when functioning as a neon light absorbing layer is preferably designed to be 50% or less, more preferably 25% or less at a wavelength of 590 nm. As the neon light absorber, a dye having an absorption maximum in a wavelength region of at least 550 to 640 nm can be used. Specific examples of the dye include cyanine, oxonol, methine, subphthalocyanine or porphyrin. Of these, porphyrins are preferred. Among them, a tetraazaporphyrin-based dye as disclosed in Japanese Patent No. 3834479 is particularly preferable from the viewpoints of good dispersibility in the pressure-sensitive adhesive layer and good heat resistance, moisture resistance, and light resistance.
Although content of a neon light absorber is not specifically limited, It is preferable that it is 0.05 to 5 weight% in an adhesive layer. If the content is more than 0.05% by weight, a sufficient neon light absorbing function can be exhibited, and if it is 5% by weight or less, a sufficient amount of visible light can be transmitted.

(4) Color correction dye The color correction function is included to adjust the color of the display filter to improve the color purity of the light emitted from the panel, the color reproduction range, and the display color when the power is turned off. Is. Since each display has a different color correction function requirement, the display is appropriately adjusted and used.
Examples of known dyes that can be used as color correction dyes include the dyes described in JP 2000-275432 A, JP 2001-188121 A, JP 2001-350013 A, JP 2002-131530 A, and the like. Can be suitably used. In addition, other dyes such as anthraquinone, naphthalene, azo, phthalocyanine, pyromethene, tetraazaporphyrin, squarylium, and cyanine that absorb visible light such as yellow light, red light, and blue light. Can be used.
The content of the color correction dye is appropriately adjusted according to the color to be corrected and is not particularly limited. Usually, it contains about 0.01 to 10% by weight in the pressure-sensitive adhesive layer.

(5) Other components The pressure-sensitive adhesive layer in the present invention may contain a crosslinking agent such as an isocyanate compound, a tackifier, and the like as desired.
In the embodiment in which the pressure-sensitive adhesive layer is directly laminated on the conductive mesh layer of the electromagnetic wave shielding sheet, it is preferable to add an antioxidant such as benzotriazole to the pressure-sensitive adhesive layer. In this case, it is possible to prevent the conductive mesh layer from being oxidized by an acid component that can be contained in the resin at the interface with the conductive mesh layer and causing a color change.
In addition, the pressure-sensitive adhesive layer may contain various dispersants, various surfactants, silane coupling agents, and the like as dispersants for improving the dispersibility of the composite tungsten oxide fine particles. Moreover, as long as the effect of the present invention is not impaired, a near infrared absorber other than the composite tungsten oxide fine particles may be included. As near infrared absorbers other than the composite tungsten oxide fine particles, inorganic near infrared absorbers such as tungsten oxides other than those represented by the above general formula, and organic near infrared absorbers such as phthalocyanine compounds and diimonium compounds Are appropriately selected and used.
Further, by adding an ultraviolet absorber in the pressure-sensitive adhesive layer, durability against ultraviolet rays of the pressure-sensitive adhesive itself or a dye such as a neon light absorber added in the pressure-sensitive adhesive can be improved. As the ultraviolet absorber, those similar to those exemplified for the transparent resin substrate are used.

(6) Formation of pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is, for example, a coating liquid for pressure-sensitive adhesive layers containing at least the specific composite tungsten oxide fine particles and the pressure-sensitive adhesive as described above in the first embodiment ( In FIG. 1), it is formed by a wet film forming method such as coating on the conductive mesh layer of the electromagnetic wave shielding sheet, and in the second embodiment (see FIG. 2) on the transparent resin substrate of the electromagnetic wave shielding sheet. can do.
In order to improve the dispersion of the specific composite tungsten oxide fine particles, the adhesive layer coating liquid uses the specific composite tungsten oxide fine particles, if necessary, a surfactant or a silane coupling agent. Then, after appropriately dispersing in a solvent to obtain a composite tungsten oxide fine particle dispersion, the dispersion and the pressure-sensitive adhesive and a solvent as necessary are further mixed to make the dispersion state of the fine particles uniform and good. Is preferred.

The pressure-sensitive adhesive layer may be formed by coating and drying the above-mentioned pressure-sensitive adhesive layer coating solution on a release sheet such as a release-treated PET film. In this case, it is preferable to protect the pressure-sensitive adhesive layer formed on the release sheet from above using the same release sheet until it is bonded to the electromagnetic wave shielding sheet.
Alternatively, the pressure-sensitive adhesive layer may be formed by extrusion molding a pressure-sensitive adhesive composition in which the specific composite tungsten oxide fine particles are uniformly dispersed. Also in this case, it is preferable to protect both surfaces of the pressure-sensitive adhesive layer with a release sheet.

In particular, when an adhesive layer is provided on the conductive mesh layer surface of the electromagnetic shielding sheet so as to flatten the irregularities of the conductive mesh layer and expose a part of the peripheral edge of the conductive mesh layer. Is intermittent coating or intermittent bonding of the adhesive layer. In order to expose a part of the peripheral edge of the conductive mesh layer, the pressure-sensitive adhesive layer is not formed on the entire surface but is formed in a pattern.
The pressure-sensitive adhesive layer 20 may be coated or bonded so that the surface of the pressure-sensitive adhesive layer is flattened while completely filling the uneven portion so that air does not enter the unevenness of the conductive mesh layer. This is preferable from the viewpoint of improving the transparency of the composite filter. Further, as a part of the peripheral portion of the conductive mesh layer to be exposed, it is sufficient to use a portion used as a grounding region as described above. Among them, the pressure-sensitive adhesive layer is preferably provided so as to expose all the four peripheral edges of the conductive mesh layer.

(7) Intermittent coating To coat the conductive mesh layer 16 so that the surface of the pressure-sensitive adhesive layer is flattened while completely filling the irregularities so that air does not enter the irregularities of the conductive mesh layer. In addition, the pressure-sensitive adhesive layer forming coating liquid preferably has fluidity when laminated on the conductive mesh layer 16. In such a case, since the pressure-sensitive adhesive layer spreads to every corner in the mesh opening when the electromagnetic wave shielding sheet and the pressure-sensitive adhesive layer are laminated, it is possible to prevent bubbles from remaining in the opening. Therefore, it is possible to avoid the inconvenience of increasing the haze of the composite filter due to light scattering of bubbles while omitting the flattening step on the mesh surface, and to obtain a highly transparent composite filter with high production efficiency. . Therefore, the fluidity of the pressure-sensitive adhesive layer in the present invention is such that the pressure-sensitive adhesive layer can flow in and replace the air in the mesh-shaped region opening to fill the opening. The fluidity of the pressure-sensitive adhesive layer in the present invention refers to the property that it does not have a restoring force with respect to an external force, or has only a small amount, and deforms and displaces indefinitely. For example, Newton viscosity such as water, non-Newton viscosity such as dilatancy or thixotropy, or creep deformability is included. As a guide, when the pressure-sensitive adhesive is applied to the mesh surface, it is preferably used so as to have a viscosity of about 1000 cps or less, preferably about 5000 cps or less (measured value with a C-type viscometer. value). However, after laminating on the mesh opening of the electromagnetic wave shielding sheet, it is preferable to lower the fluidity of the pressure-sensitive adhesive layer as necessary. That is, at the time of adhesion with the conductive mesh layer, the fluidity of the pressure-sensitive adhesive layer is preferably as high as possible in order to reliably fill the mesh opening. However, the flowability of the pressure-sensitive adhesive layer is not required after lamination, but rather the flowability of the pressure-sensitive adhesive is not preferable because the adhesive may flow out from the lamination interface or the discoloration of the light absorber or the pigment may be promoted. Because.

  In order to make the coating liquid for forming the adhesive layer have fluidity, the material constituting the adhesive layer may be diluted with a solvent, or it itself has fluidity at room temperature without containing a solvent. You may use the adhesive material which consists of a natural rubber, a synthetic resin, or a syrup type adhesive in which the polymer is melt | dissolving in the reaction monomer. Further, a hot-melt type pressure-sensitive adhesive that melts and has fluidity by appropriately applying a temperature may be used. Furthermore, it may be a pressure-sensitive adhesive layer containing a polymerization reactive monomer that is liquid at room temperature, and is a pressure-sensitive adhesive layer that is cured by light and / or heat after lamination. In addition, as a method of reducing the fluidity of the pressure-sensitive adhesive layer as necessary after adhesion and lamination, for example, the diluted solvent is dried, or a crosslinking agent is added to the pressure-sensitive adhesive layer in advance, heating, ultraviolet irradiation, etc. Can be used to crosslink or polymerize the pressure-sensitive adhesive.

Examples of the intermittent coating method include a roll coater, a die coater, a blade coater, and screen printing. In particular, in the present invention, when the pressure-sensitive adhesive layer forming coating solution is prepared and used so as to have the above fluidity, solvent dilution is preferably used.
In the case of performing intermittent coating, there is an advantage that the production speed can be easily increased and the productivity can be easily improved.

(8) Intermittent bonding First, the pressure-sensitive adhesive layer is formed on the release sheet as described above to obtain a continuous belt-shaped pressure-sensitive adhesive layer. In this case, the width of the continuous belt-shaped pressure-sensitive adhesive layer is preferably adjusted to a width that is smaller than the width of the electromagnetic shielding sheet to be bonded and slightly larger than the width of the conductive mesh layer. In this way, when the continuous belt-like pressure-sensitive adhesive layer and the continuous belt-like electromagnetic wave shielding sheet are bonded together, the width direction of the continuous belt of the periphery of the conductive mesh layer in the electromagnetic wave shielding sheet is exposed and becomes a grounding region. obtain.
When not only the continuous strip-shaped width direction among the peripheral edges of the mesh layer but also the four peripheral edges of the mesh layer are the grounding regions, intermittent bonding is performed to expose the continuous belt-shaped flow direction.
In the intermittent bonding, a continuous belt-like pressure-sensitive adhesive layer having a width appropriately narrower than the width of the electromagnetic wave shielding sheet is exposed on the conductive mesh layer surface of the continuous belt shaped electromagnetic wave shielding sheet, and the peripheral four sides of the conductive mesh layer are exposed. Bonding is performed intermittently while positioning on the conductive mesh layer while cutting into such a size.

The laminator may be a roll type, a flat type, etc., as long as it can pressurize the pressure-sensitive adhesive layer and the electromagnetic wave shielding sheet, but it can easily cope with the roll-to-roll method and prevent air bubbles from being mixed. It is preferable to use a roll-type laminator from the viewpoint of being able to be produced continuously and capable of continuous production.
Although the pressurization at the time of lamination is not particularly limited, for example, when a roll laminator is used, the linear pressure is preferably 1 to 20 kgf / cm. Although the temperature of the pressurization part at the time of lamination | stacking is also not specifically limited, From the point of an equipment burden, the one where it is low temperature is preferable and it is more preferable that it is 20 to 80 degreeC. However, you may heat to 80 degreeC or more as needed.

In addition, when intermittent bonding is performed, heating is applied so that the surface of the pressure-sensitive adhesive layer is flattened while the pressure-sensitive adhesive layer completely fills the uneven portions so that air does not enter the unevenness of the conductive mesh layer. It is preferable to perform pressure treatment. Examples of the heat vacuum treatment include performing the treatment at 50 to 100 ° C. for 10 to 90 minutes in a vacuum of 0.2 to 1.0 MPa.
When intermittent bonding is performed, there is an advantage that the apparatus is simpler and the yield is higher than that of intermittent coating. Moreover, since the magnitude | size of an adhesive layer and its protective film layer becomes the same, there exists a merit that peeling and distortion of the said protective film do not arise easily.

  The formed pressure-sensitive adhesive layer has a sticking function, so a temporary protective film such as an easily peelable PET film treated with silicone is used to prevent inadvertent adhesion until sticking to the display. It is preferable to laminate.

(9) Physical properties of the pressure-sensitive adhesive layer Further, in the present invention, the pressure-sensitive adhesive layer has a peel resistance value of 5 to 30 N / 25 mm for a smooth glass plate, 5 to 25 N / 25 mm, particularly 10 to 20 N / 25 mm. It is preferable that
Examples of the glass plate having a smooth surface include normal float glass, liquid crystal, and glass used in PDP panels.
When the peel resistance value is within the above range, there is no possibility that the resulting composite filter-display interface will be spontaneously peeled over time or bubbles may be generated. In addition, when some trouble occurs when the obtained composite filter and the display are bonded together, it is necessary to peel off only the composite filter and paste the composite filter again, but the peeling resistance value is within the above range. In this case, when the composite filter is peeled off again, it can be easily peeled off without causing cohesive failure and interface failure.

Here, the peel resistance value with respect to the smooth glass plate can be measured as follows. An adhesive layer coated at 25 g / m ² (when dried) on one side of a 100 μm-thick biaxially stretched PET film is cut out to a length of 150 mm and a width of 25 mm, and the adhesive layer side is a glass plate The glass plate and the PET film are attached to a glass plate having a thickness of 2 mm with a degreased surface facing the side, and this is pulled using a tensile tester so that the angle between the glass plate and the PET film is 180 °. It can be measured as tensile strength at the time of peeling by pulling in an atmosphere of 20 to 25 ° C. at 300 mm / min.

  In the present invention, the thickness of the pressure-sensitive adhesive layer is appropriately adjusted by an optical filter function such as a near-infrared absorption function or a function further added to the pressure-sensitive adhesive layer, but the thickness at the time of normal drying is about 20 to 50 μm. . For example, when functioning also as a planarization layer of a conductive mesh layer, it is preferable that it is in the range of 25 to 40 μm from the viewpoint of satisfactorily planarizing the mesh irregularities. Moreover, when making an adhesive layer function also as an impact-resistant layer, it is preferable to make it especially the thickness at the time of drying to be 50-5,000 micrometers in total with the adhesive layer mentioned later. In such a case, it is desirable that the fracture energy by the following impact test has an impact resistance of 0.5 J or more, preferably 0.6 J or more. Here, the impact test is performed using the impact test apparatus shown in FIG. 8, and a steel ball 125 (mass 534 g) having a diameter of 50.8 mm (specified in JIS B1501 ball bearing steel ball) is dropped from the electromagnet 124. This is done by measuring the fracture energy. Fracture energy can be changed by changing the drop height of the steel ball. A stainless steel plate is used as the test table 121. As a front glass plate 122 for a display device in which the pressure-sensitive adhesive layer 123 of the present invention is laminated on the test bench 121, for example, a high strain point glass plate manufactured by Asahi Glass Co., Ltd. (PD-200: trade name, thickness 2.8 mm). Is placed.

3. Surface Protective Layer The surface protective layer used in the present invention is a layer that protects the surface of the transparent resin substrate, and one or more functions selected from the group consisting of an antireflection function, an antiglare function, and an abrasion resistance function. It is what has. The surface protective layer may be formed as a multilayer in addition to a single layer. However, no substrate is interposed between the two or more surface protective layers of the present invention. The uppermost layer of the composite filter of the present invention has an anti-reflection function and anti-glare as a means for reducing the reflection of background due to specular reflection of extraneous light on the surface of the image display device, image whitening, and reduction in image contrast. It is preferable to impart a function, and it is preferable to form a so-called antiglare layer and / or a so-called antireflection layer. The former anti-glare layer is a technique in which light is scattered or diffused like a polished glass to make a background image by extraneous light. As the latter antireflection layer, a material with a high refractive index and a material with a low refractive index are alternately laminated and multilayered so that the outermost surface is a low refractive index layer (multi-coat), and the reflected light at the interface of each layer is reflected. This is a technique for suppressing surface reflection and obtaining a good antireflection effect by canceling out by interference, which is a so-called antireflection layer in a narrow sense.
Moreover, you may make a surface protective layer contain an ultraviolet absorber from the point which brings a ultraviolet-ray shielding function to a composite filter.

(1) Antiglare layer The antiglare layer (Anti Glare layer, abbreviated as AG layer) basically has a light incident surface roughened to scatter or diffuse extraneous light. For this roughening treatment, a method of forming a rough surface directly on the surface of the substrate by sandblasting or embossing or the like; and roughening the surface of the substrate with a resin binder that is cured by radiation or heat, or a combination thereof, Examples include a method of providing a roughened layer with a coating film containing an inorganic filler such as silica or an organic filler such as resin particles as light diffusing particles; and a method of forming a porous film with a sea-island structure on the surface of the substrate. be able to. As the resin for the resin binder, a curable acrylic resin, an ionizing radiation curable resin, or the like is preferably used in the same manner as the hard coat layer because surface strength is desired as the surface layer.
The thickness of the antiglare layer is not particularly limited, but is preferably 0.07 μm or more and 20 μm or less.

(2) Antireflective layer The antireflective layer (Anti Reflection layer, abbreviated as AR layer) is a single low refractive index layer or a low refractive index layer and a high refractive index layer. A multilayer structure in which layers are alternately stacked so as to be positioned at the uppermost layer is generally used, and can be formed by a dry film formation method such as vapor deposition or sputtering, or by using a wet film formation method such as coating. Note that silicon oxide, magnesium fluoride, fluorine-containing resin, or the like is used for the low refractive index layer, and titanium oxide, zinc sulfide, zirconium oxide, niobium oxide, or the like is used for the high refractive index layer. Here, the high (low) refractive index layer means that the refractive index of the layer is relatively higher than that of a layer adjacent to the layer (for example, a transparent resin substrate or a low (high) refractive index layer). It means high (low).
When the antireflection layer is further provided with a scratch resistance function, it is formed by appropriately using a material having high hardness as described in the section of the scratch resistance function (hard coat) layer.

In order to improve the antireflection effect, the refractive index of the low refractive index layer is preferably 1.45 or less. Examples of the material having these characteristics include LiF (refractive index n = 1.4), MgF ₂ (refractive index n = 1.4), 3NaF · AlF ₃ (refractive index n = 1.4), AlF ₃ ( Inorganic materials such as refractive index n = 1.4), Na ₃ AlF ₆ (refractive index n = 1.33), SiO ₂ (refractive index n = 1.45) are made into fine particles, acrylic resin, epoxy resin, etc. Inorganic low-reflective materials, fluorine-based / silicone-based organic compounds, thermoplastic resins, thermosetting resins, radiation-curable resins, and the like can be used.
Further, fine particles having voids may be used for the low refractive index layer. The fine particles having voids form a structure in which fine particles are filled with gas and / or a porous structure containing gas, and are in inverse proportion to the gas occupancy ratio in the fine particles compared to the original refractive index of the fine particles. It means fine particles having a reduced refractive index. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is. The fine particles having voids may be either inorganic or organic, and examples thereof include metals, metal oxides, and resins, and preferably silicon oxide (silica) fine particles.

Furthermore, a material in which a sol obtained by dispersing ultrafine silica particles of 5 to 30 nm in water or an organic solvent and a fluorine-based film forming agent can be used. The sol in which the ultrafine silica particles of 5 to 30 nm are dispersed in water or an organic solvent is obtained by a method of dealkalizing alkali metal ions in alkali silicate salt by ion exchange or the like, or neutralizing alkali silicate salt with mineral acid. A known silica sol obtained by condensing active silicic acid known by the method, etc., a known silica sol obtained by condensing alkoxysilane with hydrolysis in an organic solvent in the presence of a basic catalyst, and the above-mentioned An organic solvent-based silica sol (organosilica sol) obtained by substituting water in the aqueous silica sol with an organic solvent by a distillation method or the like is used. These silica sols can be used in both aqueous and organic solvent systems. In producing the organic solvent-based silica sol, it is not necessary to completely replace water with the organic solvent. The silica sol contains solids 0.5 to 50 wt% concentration as SiO _2. Various structures such as a spherical shape, a needle shape, and a plate shape can be used for the structure of the ultrafine silica particles in the silica sol. As the film forming agent, alkoxysilane, metal alkoxide, hydrolyzate of metal salt, or fluorine-modified polysiloxane can be used. According to a preferred embodiment of the low refractive index layer, “fine particles having voids” are preferably used.

  The low refractive index layer is obtained by diluting the above-described material into a solvent, for example, a wet coating method such as spin coating, roll coating or printing, or a vapor phase method such as vacuum deposition, sputtering, plasma CVD, or ion plating. After being provided on the high refractive index layer and dried, it can be obtained by curing with heat or radiation (in the case of ultraviolet rays, the above-mentioned photopolymerization initiator is used).

  The high refractive index layer is formed by using a binder resin having a high refractive index in order to increase the refractive index, adding ultrafine particles having a high refractive index to the binder resin, or using these in combination. To do. The refractive index of the high refractive index layer is preferably in the range of 1.55 to 2.70.

  As the resin used for the high refractive index layer, any resin can be used as long as it is transparent, and a thermosetting resin, a thermoplastic resin, a radiation (including ultraviolet) curable resin, or the like can be used. Thermosetting resins include phenolic resin, melamine resin, polyurethane resin, urea resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polysiloxane resin, etc. A curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be added to these resins as necessary.

As the ultrafine particles having a high refractive index, for example, ZnO (refractive index n = 1.9), TiO ₂ (refractive index n = 2.3 to 2.7), which can also obtain an ultraviolet shielding effect, Fine particles of CeO ₂ (refractive index n = 1.95), antimony-doped SnO ₂ (refractive index n = 1.95) or antistatic effect, which can prevent the adhesion of dust or Examples thereof include fine particles of ITO (refractive index n = 1.95). Other fine particles include Al ₂ O ₃ (refractive index n = 1.63), La ₂ O ₃ (refractive index n = 1.95), ZrO ₂ (refractive index n = 2.05), Y ₂ O _3. (Refractive index n = 1.87). These fine particles are used singly or in combination, and those in the form of a colloid dispersed in an organic solvent or water are good in terms of dispersibility, and the particle size is 1 to 100 nm, the transparency of the coating film To preferably 5 to 20 nm.
In order to provide the high refractive index layer, the material described above is diluted with a solvent, for example, provided on a substrate by a method such as spin coating, roll coating, or printing, dried, and then subjected to heat or radiation (in the case of ultraviolet rays, the above-mentioned). The photopolymerization initiator may be used for curing.
The thickness of the antireflection layer is not particularly limited, but is usually about ¼ (95 to 195 nm) of the wavelength of visible light (380 to 780 nm) to be antireflection.

(3) Scratch-resistant functional layer The scratch-resistant (hard coat) layer preferably exhibits a hardness of “H” or higher in a pencil hardness test specified by JISK5600-5-4 (1999). The material is not particularly limited as long as it can achieve the same hardness and the same transparency as the transparent resin substrate.
The scratch-resistant (hard coat) layer is usually formed as a cured resin layer. As the curable resin to be used, an ionizing radiation curable resin, other known curable resins, or the like may be appropriately employed according to required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins. For example, acrylate-based ionizing radiation curable resins are, for example, polyfunctional (meth) acrylate prepolymers such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, or trimethylolpropane tri (meth) ) Trifunctional or higher polyfunctional (meth) acrylate monomers such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., alone or in combination of two or more selected from these It can be formed as a coating film using an ionizing radiation curable resin. Here, (meth) acrylate is a composite notation meaning acrylate or methacrylate. The scratch resistance function (hard coat) can be formed by a wet film formation method such as coating on the transparent resin substrate by diluting the material with a solvent as necessary.
The thickness of the scratch-resistant functional layer is not particularly limited, but is preferably 1.0 μm or more and 20 μm or less, more preferably 3.0 μm or more and 5 μm or less.

(4) Ultraviolet absorbing layer In the present invention, the ultraviolet absorbing layer is prepared by adding an ultraviolet absorber to the pressure sensitive adhesive layer itself in order to prevent deterioration of the light absorbent contained in the pressure sensitive adhesive layer according to the present invention. The ultraviolet absorbing layer and the pressure-sensitive adhesive layer may be used together, or a layer (including a base material) independent of the pressure-sensitive adhesive layer may be disposed on the observation side of the pressure-sensitive adhesive layer. As described above, the surface protective layer is provided in addition to the aspect of imparting an ultraviolet absorbing function to the transparent resin substrate of the electromagnetic wave shielding sheet. The surface protective layer having the other functions described above may contain a UV absorber, and may be a layer having another function and an UV absorbing function, or may be an independent UV absorbing layer. As the ultraviolet absorber used in the functional layer, the same ultraviolet absorber as that described in the transparent resin substrate of the electromagnetic wave shielding sheet according to the present invention can be used. As the binder resin used for the independent layer, a resin such as a polyester resin, a polyurethane resin, an acrylic resin, or an epoxy resin is used.
Also, commercially available UV cut filters such as “Sharp Cut Filter SC-38” (trade name), “SC-39”, “SC-40” manufactured by Fuji Photo Film Co., Ltd., “Acryprene” manufactured by Mitsubishi Rayon Co., Ltd. (Product name) or the like can also be used.
Although the thickness of an ultraviolet absorption layer is not specifically limited, 1.0 micrometer or more and 30 micrometers or less are preferable, More preferably, they are 10 micrometers or more and 20 micrometers or less.

(5) Other functions In addition, the surface protective layer may be added with a silicone compound, a fluorine compound, or the like in terms of improving the stain resistance.
The surface protective layer also prevents or adheres to dirt and contaminants due to inadvertent contact and environmental contamination when using a composite filter as a pollution control layer. Alternatively, a layer formed to facilitate removal may be used. For example, a fluorine-based coating resin, a silicon-based coating agent, a silicon / fluorine-based coating agent, or the like is used, and among them, a silicon / fluorine-based coating agent is preferably applied. The thickness of these antifouling layers is preferably 100 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. When the thickness of these antifouling layers exceeds 100 nm, the initial value of antifouling properties is excellent, but the durability is inferior. 5 nm or less is the most preferable from the balance of antifouling property and its durability.

Moreover, it is preferable that the surface protective layer used in the present invention is formed as a single layer having a plurality of functions.
For example, in addition to the scratch resistance function, it may have a function of preventing specular reflection of extraneous light. Specifically, the scratch-resistant functional layer is an antiglare layer or an antireflection layer. For example, in the case of an antiglare layer, the surface protective layer is formed with the above-described light diffusing particles in the uppermost scratch-resistant functional layer, and the surface of the scratch-resistant functional layer is roughened. The form can be mentioned.
In addition, in order to make the surface rough by shaping, after applying the resin composition for forming the scratch-resistant functional layer on the transparent resin base material surface or the conductive mesh surface of the electromagnetic wave shielding sheet, or at the time of application When the resin is cured, the surface may be shaped with a shaped sheet or a shaped plate while it has fluidity that can be shaped before complete curing.
Further, when the antireflection layer is used, it is only necessary to lower the refractive index of the scratch-resistant functional layer, which is the uppermost layer in the surface protective layer, by a method as described in the above antireflection layer than the layer immediately below the antireflection layer. .

(6) Formation of surface protective layer The surface protective layer can be formed in the same manner as the above-mentioned pressure-sensitive adhesive layer. For example, when the surface protective layer is formed on the conductive mesh layer of the electromagnetic wave shielding sheet, it is preferable that intermittent coating or intermittent bonding is performed under the above-described conditions.

4). Characteristics of Composite Filter As described above, each layer has been described as an example. However, when the composite filter of the present invention is applied to the front surface of a plasma display panel which is a typical application, the plasma display panel uses xenon gas discharge. The light transmittance in the near-infrared region generated when emitting light, that is, in the wavelength region of 800 to 1100 nm is preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less.
In addition, when the composite filter of the present invention is applied to the front surface of a plasma display panel which is a typical application, the neon atom is excited when the plasma display panel emits light using xenon gas discharge. The neon light emitted when returning to the ground state, that is, the light transmittance at a wavelength of 590 nm is preferably 50% or less, more preferably 25% or less.
In addition, the composite filter of the present invention desirably has a sufficient light transmittance, that is, a visible light transmittance of 30% or more, and further 40% or more in a visible light region, that is, a wavelength region of 380 to 780 nm.
The light transmittance in the present invention can be measured with a spectrophotometer (for example, product number: UV-3100PC, company name: Shimadzu Corporation) in accordance with JIS-Z8701.

  The composite filter of the present invention has an excellent optical filter function durability, and the spectral characteristics attributed to the deterioration of the light absorber hardly occur even when used for a long time under high temperature and high humidity. Specifically, the initial state of the produced composite filter, the normal environment of the composite filter (23 ° C., humidity 60% or less), the heat resistant environment (80 ° C., humidity 10% or less), and the moisture and heat resistant environment (60 ° C. 95%) Comparison of spectral characteristics (transmittance T, chromaticity (x, y)) after 1000 hours under three conditions (RH), the transmittance change ΔT at 380 nm to 1000 nm is 20% or less. Further, it is preferably 10% or less, and the transmittance change ΔT at 800 nm to 1000 nm is preferably 10% or less, and more preferably 5% or less. Further, the changes Δx and Δy in the chromaticity (x, y) of the composite filter are both 0.03 or less, more preferably 0.02 or less.

  The film thickness of the composite filter for display according to the present invention described above can be made thin because the substrate used is substantially one layer, and is within the range of 100 to 1000 μm, and further within the range of 200 to 500 μm. It is preferable that By setting it as such a range, since it becomes possible to wind in a roll shape whose minimum diameter is 15 centimeters or less as a continuous belt shape, production efficiency improves.

  The composite filter for display according to the present invention described above is coated so that the surface is flattened while completely filling the uneven portion so that air does not enter the uneven portion of the conductive mesh layer, In addition, by appropriately selecting a resin that reduces the haze of the near-infrared absorbing layer, a highly transparent one can be obtained. Specifically, the haze is preferably 10 or less, more preferably 5 or less. Here, haze means a value measured by a method based on JIS K7136.

5. Production method of composite filter The production method of the composite filter is not particularly limited, but preferably, a continuous belt-like material is prepared as a transparent resin substrate, and this is continuously or intermittently run in a continuous belt shape. Thus, it is preferable to form necessary layers continuously or intermittently. That is, it is preferable in terms of productivity to manufacture by so-called roll-to-roll processing. In that case, it is more preferable to carry out all the steps up to the last layer lamination continuously with one machine.

The order of forming the layers is not particularly limited as long as it is appropriately selected according to the embodiment, and may be appropriately determined according to the specification. Examples include the following.
First, prepare a transparent resin base material.
(A): 1. 1. Formation of surface protective layer 2. formation of a conductor layer and subsequent formation of a conductive mesh layer; Formation of an adhesive layer.
(B): 1. 1. formation of a conductor layer and subsequent formation of a conductive mesh layer; 2. Formation of surface protective layer Formation of an adhesive layer.
(C): 1. 1. formation of a conductor layer; 2. Formation of surface protective layer 3. formation of a conductor mesh layer from the conductor layer; Formation of an adhesive layer.
Etc.

In the case where the pressure-sensitive adhesive layer or the surface protective layer is partially formed on the conductive mesh layer, it is also formed on a part of the grounding region, usually on the inner part of the mesh region. The reason for this is to ensure that the mechanically weak mesh region can be reliably protected even if there is a slight misalignment.
Then, a plurality of one unit composite filters corresponding to one unit of display to be applied, which are manufactured in a continuous band shape in this way, are cut into single sheets by cutting each unit of the composite filter. .

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.

<Example 1>
(Manufacture of electromagnetic shielding sheets)
As a transparent resin substrate, a continuous strip-shaped uncolored transparent biaxially stretched polyethylene terephthalate (PET) film (A4300: trade name, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was prepared. Next, a blackened layer (Ni—Cu—O blackened layer) made of an alloy containing nickel, copper and oxygen was formed on the PET surface by vacuum sputtering. Copper conductors were deposited thereon to laminate a conductor layer. The sheet resistance was 0.01Ω / □.
Next, in the above laminate, the conductor layer and the blackened layer are etched using a photolithography method, and a PDP image display using a transparent conductor layer composed of a mesh-like region composed of openings and line portions is displayed. A transparent conductive layer was formed corresponding to the region, and a conductive mesh layer having a frame-shaped mesh-free grounding region was formed on the outer edge surrounding the circumference of the mesh region. The mesh shape was a square lattice having square openings, the line width was 10 μm, and the opening width (side length of the square) was 290 μm. One rectangular area having the mesh shape corresponds to one screen of the PDP. Such rectangular mesh-like regions are arranged on one side at intervals of 30 mm in the form of a continuous band, and margins having a width of 15 mm are formed on both sides of the arrangement of the mesh-like regions, and the width of the grounding region at the peripheral portion is increased. It was 15 mm.
Specifically, the etching was performed consistently from resist formation, masking to etching on the laminate using a production line for a color TV shadow mask. That is, after a photosensitive etching resist is applied to the entire surface of the transparent conductor layer of the laminate, a mask with a desired mesh pattern is closely exposed, developed, hardened, and baked to correspond to a mesh line portion. After processing the resist layer into a pattern in which the resist layer remains on the region and there is no resist layer on the region corresponding to the opening, the conductive layer in the region where the resist layer is not formed with an aqueous ferric chloride solution Then, the blackened layer was removed by etching to form a mesh-shaped opening, followed by sequential washing with water, stripping of the resist, washing and drying.

(Process of laminating an antiglare layer on the surface of the electromagnetic shielding sheet on the transparent resin substrate side)
An antiglare layer was formed on the surface of the electromagnetic wave shielding sheet on the transparent resin substrate side. Specifically, first, as an ionizing radiation curable resin, 70 parts by mass of pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.49) and 30 parts by mass of isocyanuric acid EO-modified diacrylate (Toago) 10.0 parts by mass of Synthetic Co., Ltd., refractive index 1.51), acrylic polymer (Mitsubishi Rayon Co., Ltd., molecular weight: 75,000), 5.0 of the trade name Irgacure 184 as a photocuring initiator In addition, 15.0 parts by mass of styrene beads (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index) as an ultraviolet curable resin blended with parts by mass (Ciba Gaigi Co., Ltd.) 1.60), 0.01 part by mass (made by The Inktec Co., Ltd.) as a trade name “10-28” as a leveling agent, 127.5 parts by mass of toluene, and 54.6 parts by mass of cyclohexanone, And a coating solution was thoroughly mixed. This coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for forming an antiglare layer. Next, the coating solution is applied on the surface of the electromagnetic shielding sheet on the transparent resin substrate side so as to have a film thickness of 7 μm, and then heated and dried in an oven at 50 ° C., and UV is applied in an N ₂ atmosphere. Using an H bulb of an irradiation apparatus (manufactured by Fusion UV System Japan Co., Ltd.) as a light source, it was cured by ultraviolet irradiation (integrated light amount 200 mj) to form an antiglare layer.

(Formation of adhesive layer)
Next, the adhesive layer which added various light absorbers to the surface by the side of the electroconductive mesh layer of the electromagnetic wave shielding sheet with the antiglare layer already formed was formed. For 100 parts by weight of acrylic adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 2094), 0.25 parts by weight of curing agent (manufactured by Soken Chemical Co., Ltd., E-5XM), cesium-containing tungsten oxide (Cs _{0. 33} WO ₃ ) 18.5 wt% suspension (manufactured by Sumitomo Metal Mining Co., Ltd., YMF-02; average dispersed particle size 800 nm or less) 1.32 parts by weight, neon light absorber (manufactured by Yamada Chemical Co., Ltd.) , TAP-2; tetraazaporphyrin-based dye) 0.045 parts by weight, and color correction dye (Nippon Kayaku Co., Ltd., KAYASET RED A2G) 0.3 parts by weight are added and dispersed sufficiently to form an adhesive layer composition. Was prepared.
Next, it apply | coats with respect to the surface at the side of the electroconductive mesh layer of the said laminated body so that it may become thickness 25micrometer at the time of drying with a die coater, and it is 100 degreeC for 1 minute in the oven which hits dry air with a wind speed of 5 m / sec. The pressure-sensitive adhesive layer was formed by drying, and a composite filter was obtained in a continuous belt-like state. The surface of the pressure-sensitive adhesive layer was further protected by attaching a releasable release film.
The pressure-sensitive adhesive layer was partially formed by an intermittent coating method so as not to cover the grounding region surrounding the periphery of the conductive mesh layer but to cover the mesh region.

(Lamination on PDP panel)
The release film of the electromagnetic wave shielding sheet was peeled off and directly bonded to a PDP panel to obtain a plasma TV.

<Example 2>
The electromagnetic shielding sheet was produced in the same manner as in Example 1.

(Process of laminating an antiglare layer on the surface of the electromagnetic shielding sheet on the conductive mesh layer side)
An antiglare layer was formed on the surface of the electromagnetic wave shielding sheet on the conductive mesh layer side. Specifically, first, as an ionizing radiation curable resin, 70 parts by mass of pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.49) and 30 parts by mass of isocyanuric acid EO-modified diacrylate (Toago) 10.0 parts by mass of Synthetic Co., Ltd., refractive index 1.51), acrylic polymer (Mitsubishi Rayon Co., Ltd., molecular weight: 75,000), 5.0 of the trade name Irgacure 184 as a photocuring initiator In addition, 15.0 parts by mass of styrene beads (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index) as an ultraviolet curable resin blended with parts by mass (Ciba Gaigi Co., Ltd.) 1.60), 0.01 part by mass (made by The Inktec Co., Ltd.) as a trade name “10-28” as a leveling agent, 127.5 parts by mass of toluene, and 54.6 parts by mass of cyclohexanone, And a coating solution was thoroughly mixed. This coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for forming an antiglare layer. Next, the coating solution is applied on the surface of the electromagnetic shielding sheet on the side of the conductive mesh layer so as to have a film thickness of 10 μm, and then heated and dried in an oven at 50 ° C., and UV is applied in an N ₂ atmosphere. Using an H bulb of an irradiation apparatus (Fusion UV System Japan Co., Ltd.) as a light source, it was cured by ultraviolet irradiation (integrated light amount 200 mj) to form an antiglare layer.

(Formation of adhesive layer)
Next, the adhesive layer which added various light absorbers was formed with respect to the surface at the side of the transparent resin base material of the above-mentioned continuous anti-glare sheet with the antiglare layer formed. For 100 parts by weight of acrylic adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 2094), 0.25 parts by weight of curing agent (manufactured by Soken Chemical Co., Ltd., E-5XM), cesium-containing tungsten oxide (Cs _{0. 33} WO ₃ ) 18.5 wt% suspension (manufactured by Sumitomo Metal Mining Co., Ltd., YMF-02; average dispersed particle size 800 nm or less) 1.32 parts by weight, neon light absorber (manufactured by Yamada Chemical Co., Ltd.) , TAP-2; tetraazaporphyrin-based dye) 0.045 parts by weight, and color correction dye (Nippon Kayaku Co., Ltd., KAYASET RED A2G) 0.3 parts by weight are added and dispersed sufficiently to form an adhesive layer composition. Was prepared.
Next, it apply | coats with respect to the surface at the side of the electroconductive mesh layer of the said laminated body so that it may become thickness 25micrometer at the time of drying with a die coater, and it is 100 degreeC for 1 minute in the oven which hits dry air with a wind speed of 5 m / sec. The pressure-sensitive adhesive layer was formed by drying, and a composite filter was obtained in a continuous belt-like state. The surface of the pressure-sensitive adhesive layer was further protected by attaching a releasable release film.

(Lamination on PDP panel)
The release film of the electromagnetic wave shielding sheet was peeled off and directly bonded to a PDP panel to obtain a plasma TV.

<Example 3>
The release film of the electromagnetic wave shielding sheet produced in Example 1 was peeled off, bonded to a blue plate glass having a thickness of 2.5 mm, and set on the viewer side of the PDP panel to obtain a plasma TV.

<Comparative Example 1>
An antiglare layer was laminated on one surface of the transparent resin substrate in the same manner as in Example 1 to prepare an antiglare film. Next, the pressure-sensitive adhesive composition prepared in Example 1 was applied to the transparent resin substrate surface of the antiglare film and dried at 100 ° C. for 1 minute in an oven exposed to dry air with a wind speed of 5 m / sec. A layer was formed. This was bonded to one surface of a 2.5 mm thick glass plate using a single wafer bonding machine (manufactured by Suntec).
Further, the adhesive TU-41A (manufactured by Yodogawa Paper Mill) was laminated on the surface of the electromagnetic wave shielding sheet of Example 1 on the side of the transparent resin substrate, and the glass plate on which the above-described antiglare film was bonded was reversed. Above, it bonded together so that the other surface of the said glass plate might be similarly stuck using the sheet | seat bonding machine (made by Suntec), and the electroconductive layer of an electromagnetic wave shielding sheet might face the outer side of a glass plate. This was set on the viewer side of the PDP panel to obtain a plasma TV.
About this comparative example, in addition to using two transparent resin base materials, since both sides were stuck on a glass plate, the number of processes increased and it was complicated.

It is sectional drawing which showed typically an example of the composite filter for a display which concerns on this invention. It is sectional drawing which showed typically another example of the composite filter for a display which concerns on this invention. FIG. 3A is a plan view schematically showing an example of an electromagnetic wave shielding sheet used in the present invention. FIG. 3B is a cross-sectional view schematically showing an example of the electromagnetic wave shielding sheet used in the present invention. FIG. 4A is a cross-sectional view schematically showing an example of a layer configuration of a conductor layer according to the present invention. FIG. 4B is a cross-sectional view schematically showing another example of the layer configuration of the conductor layer according to the present invention. FIG. 4C is a cross-sectional view schematically showing another example of the layer configuration of the conductor layer according to the present invention. It is the perspective view which showed typically an example of the mesh of the electromagnetic wave shielding sheet used for this invention. It is the flow sheet which showed an example of the manufacturing method of the electromagnetic wave shielding sheet which concerns on this invention. It is the flow sheet which showed another example of the manufacturing method of the electromagnetic wave shielding sheet which concerns on this invention. It is a figure which shows the impact test apparatus used in performing the impact resistance test of this invention. FIG. 9A is a cross-sectional view schematically showing an example of a layer configuration of a conductor layer of a conventional electromagnetic wave shielding sheet. FIG. 9B is a diagram schematically illustrating an example of a method of using a conventional electromagnetic wave shielding sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display composite filter 10 Electromagnetic wave shielding sheet 11 Transparent resin base material 13 Blackening layer 14 Copper sputter layer 15 Copper plating layer 16 Conductive mesh layer 18 Underlayer 20 Adhesive layer 30 Surface protective layer 40 Plasma display 50 Viewer 101 Mesh Area 102 Non-mesh area 103 Opening 104A, 104B Line 115 Electromagnetic wave shielding sheet 121 Test stand 122 Glass plate 124 Electromagnet 125 Steel ball

Claims (19)

On one surface of the transparent resin substrate, an electromagnetic wave shielding sheet having at least a plurality of openings and a conductive mesh layer having a line portion surrounding and partitioning the openings, an adhesive layer on one surface, and the other A surface protective layer having one or more functions selected from the group consisting of an antireflection function, an antiglare function, and a scratch resistance function is formed on the surface,
The conductive mesh layer has a laminated structure including a conductor layer and a blackened layer provided on at least the transparent resin substrate side of the conductor layer, and the blackened layer is formed of nickel, copper, and oxygen. A blackened layer (Ni-Cu-O blackened layer) made of an alloy containing
The pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, A composite filter for a display comprising composite tungsten oxide fine particles represented by 2.2 ≦ z / y ≦ 3.0).   The composite filter for display according to claim 1, wherein a part of a peripheral edge of the conductive mesh layer is exposed.   The pressure-sensitive adhesive layer containing composite tungsten oxide fine particles is formed directly on the surface of the electromagnetic wave shielding sheet on the conductive mesh layer side without any other layer, and the transparent resin base material of the electromagnetic wave shielding sheet A surface protective layer having at least one function selected from the group consisting of an antireflection function, an antiglare function, and an abrasion resistance function is formed on a surface that does not have a conductive mesh layer, and the electromagnetic wave shielding sheet The composite filter for display according to claim 1, wherein the surface of the conductive mesh layer in the transparent resin base material side has the Ni—Cu—O blackening layer.   A surface protective layer having at least one function selected from the group consisting of an antireflection function, an antiglare function, and a scratch resistance function is formed on the surface of the electromagnetic shielding sheet on the conductive mesh layer side, and the electromagnetic shielding sheet An adhesive layer containing composite tungsten oxide fine particles is formed on the other surface of the transparent resin substrate that does not have a conductive mesh layer, and the conductive mesh layer in the electromagnetic wave shielding sheet is at least 3. The composite filter for display according to claim 1, wherein the surface opposite to the transparent resin substrate side has the Ni—Cu—O blackening layer. 4.   The composite filter for display according to any one of claims 1 to 4, wherein the transparent resin substrate, the surface protective layer, and / or the pressure-sensitive adhesive layer contains an ultraviolet absorber.   The display-use composite filter according to claim 1, wherein the pressure-sensitive adhesive layer contains a neon light absorber and / or a color correction pigment.   The composite filter for display according to any one of claims 1 to 6, wherein an average dispersed particle size of the composite tungsten oxide fine particles is 800 nm or less.   The composite filter for a display according to any one of claims 1 to 7, wherein the composite tungsten oxide fine particles include one or more kinds of crystal structures of hexagonal crystal, tetragonal crystal, and cubic crystal.   The element M in the composite tungsten oxide fine particles is a Cs (cesium) element, and the composite tungsten oxide fine particles have a hexagonal crystal structure. Composite filter for display.   The surface of the composite tungsten oxide fine particles is coated with an oxide containing one or more elements selected from Si, Ti, Zr, and Al. A composite filter for display as described in 1.   The conductive mesh layer is arranged in this order from the side close to the transparent resin substrate, the Ni—Cu—O blackening layer, the metal thin film layer formed by vapor deposition, and the metal layer as a conductor. The composite filter for a display according to claim 3, wherein the composite filter has a laminated structure laminated with each other.   In the conductive mesh layer, the metal thin film layer formed by vapor deposition, the metal layer, and the Ni—Cu—O blackening layer are laminated in this order from the side close to the transparent resin substrate. The composite filter for display according to claim 4, wherein the composite filter has a laminated structure.   The composite filter for display according to any one of claims 1 to 12, wherein the Ni-Cu-O blackening layer is a thin film layer formed by vapor deposition.   The composite filter for display according to any one of claims 1 to 13, wherein the Ni-Cu-O blackening layer has a thickness of 80 to 300 mm.   The composite filter for display according to any one of claims 1 to 14, wherein the conductor layer is a copper plating layer.   The copper plating layer has a (111) plane strength when the abundance ratio of crystal planes parallel to the surface of the copper plating layer is expressed by a plane index peak ratio of crystal planes specified by X-ray diffraction measurement. The composite filter for display according to claim 15, wherein a ratio of (200) plane strength is 50% or more.   The copper plating layer has a (111) plane strength when the abundance ratio of crystal planes parallel to the surface of the copper plating layer is expressed by a plane index peak ratio of crystal planes specified by X-ray diffraction measurement. The composite filter for display according to claim 15, wherein the (220) surface intensity ratio is 50% or more.   The copper plating layer has a (111) plane strength when the abundance ratio of crystal planes parallel to the surface of the copper plating layer is expressed by a plane index peak ratio of crystal planes specified by X-ray diffraction measurement. The composite filter for display according to claim 15, wherein the ratio of the total intensity of the (200) plane and the (220) plane is 70% or more. On one surface of the transparent resin substrate, an electromagnetic wave shielding sheet having at least a plurality of openings and a conductive mesh layer having a line portion surrounding and partitioning the openings, an adhesive layer on one surface, and the other A surface protective layer having one or more functions selected from the group consisting of an antireflection function, an antiglare function, and a scratch resistance function is formed on the surface,
The conductive mesh layer has a laminated structure including a metal layer as a conductor and a blackened layer provided on at least the transparent resin substrate side of the metal layer, and the blackened layer is made of nickel and copper. And a blackening layer (Ni-Cu-O blackening layer) made of an alloy containing oxygen,
The pressure-sensitive adhesive layer has a general formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0), which is a method for producing a composite filter for display containing composite tungsten oxide fine particles,
A step of forming a metal plating layer as the metal layer on one surface of the transparent resin base material with respect to the transparent resin base material, nickel and copper by sputtering with a Ni—Cu alloy target in the presence of oxygen gas And a step of forming a blackening layer (Ni-Cu-O blackening layer) made of an alloy containing oxygen and a step of forming another layer to be included in the conductor layer in a predetermined order, After forming a non-mesh conductor layer having a laminated structure including a metal plating layer and a Ni—Cu—O blackening layer, etching the conductor layer into a predetermined mesh shape, forming a surface protective layer The manufacturing method of the composite filter for a display characterized by including the process of forming and the process of forming an adhesive layer.

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