JP2009076654A - Electromagnetic shielding material for display, and optical filter for display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electromagnetic shielding material for display, which is superior in visibility and manufactured with high productivity at low cost on the whole, and to provide an optical filter for display using the same. <P>SOLUTION: The electromagnetic shielding material for display has a peeling-processed peeling film stacked on one surface of a transparent base 1 with an adhesive layer interposed therebetween and also has a metal mesh pattern 6, comprising a fine-wire mesh pattern 3 of development silver produced by a photographic process and a plating layer 4 stacked thereupon, formed on the other surface of the transparent base. Here, the metal mesh pattern 6 corresponds to the screen size of a display, a surface of the plating layer 4 is blackened, and resin for transparency processing is not embedded in a recessed portion of the metal mesh pattern 6, which in turn is exposed to come into contact with outside air. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electromagnetic wave shielding material for display used for various displays such as CRT and PDP (plasma display), and an optical filter for display using the electromagnetic wave shielding material for display.

  In recent years, in displays such as CRTs and PDPs (plasma displays), electromagnetic waves generated from the front of the display adversely affect the human body and malfunction of surrounding electronic devices has become a problem. Along with vividness, countermeasures against the influence of the display on the surroundings are becoming increasingly important.

In particular, in PDPs where demand is increasing as large thin displays, in addition to electromagnetic wave shielding films, near-infrared absorbing films for preventing misoperation of various remote control switches using the near-infrared wavelength region, UV light absorbing film used to prevent near-infrared absorbers used in the near infrared absorbing film from aging, neon light cut film for adjusting color tone in the visible light region, and external light reflected on the surface of the optical filter An antireflection film or the like for preventing intrusion is combined and configured according to a required function.
For example, Patent Document 1 discloses an optical filter for plasma display in which a metal mesh having electromagnetic wave shielding properties, a near-infrared absorber-containing adhesive layer having near-infrared absorption capability, an antireflection layer, and a neon light absorption layer are laminated. Is disclosed.

  On the other hand, as PDPs and the like become popular in large quantities, there is a demand for products that are cheaper and maintain high quality, and there is a need for an optical filter for display that can be manufactured at low cost by increasing productivity. .

  In the prior art, when a transparent film is bonded to the surface of a metal mesh for electromagnetic wave shielding via an adhesive, the metal mesh has irregularities, so bubbles are trapped in the concave parts, and the light is turbid. Because it becomes a display filter with insufficient properties, a transparent resin is preliminarily embedded in the concave part of the metal mesh, and after the bonding, bubbles are not bitten and transparent processing is performed without turbidity. Not only increases, but also the cost is high due to the low yield.

As a method for solving this problem, a release film surface of the release film is placed on the surface of the metal mesh, and the metal mesh is transparently bonded with a mirror roll at a temperature of 130 ° C. and a linear pressure of 25 kg / cm ^2. A method of embedding in a layer and flattening is disclosed (see Patent Document 1).
Furthermore, as another solution, a low-cost display filter with excellent translucency can be obtained by pressurizing a laminate in which a transparent base material is laminated on a metal mesh via an adhesive, thereby eliminating transparency. Has been disclosed (see Patent Document 2).

In addition, as a method of ensuring the clarity of the image on the display, the metal mesh of the electromagnetic wave shielding material reflects the light emitted from the display screen of the PDP and returns to the display screen, thereby reducing the visibility of the display screen. A method for preventing this is disclosed in Patent Document 3.
JP 2004-333743 A JP 2004-117545 A JP 2002-009484 A

In Patent Documents 1 and 3 described above, an etching mesh formed by etching a metal foil bonded to a transparent substrate can be used as the electromagnetic shielding material.
In Patent Document 2, as a method for forming a metal mesh of an electromagnetic shielding material, (1) a printed mesh printed with conductive ink, and (2) a fiber mesh obtained by bonding a knitted fabric made of conductive fibers with an adhesive. (3) Metal foil etching mesh, (4) A metal mesh formed by a known method such as a deposited film etching mesh formed by laminating a plating layer on a metal thin film formed by sputtering or the like. It can be used.

  However, as a method for forming the metal mesh pattern of the electromagnetic shielding material, the etching method is used to leave only a small portion that becomes a thin line portion by etching and dissolve and remove most other metals. It is a problem from the viewpoint of saving resources. In addition, there is a problem that the cost for treating the waste liquid generated by the etching method increases.

Moreover, in the printing mesh which printed the conductive ink, there existed a problem that adhesiveness with a transparent base material was low and it peeled easily.
Furthermore, the etching mesh for the deposited film has a problem that the equipment investment is excessive and cannot be easily implemented.

  By the way, in Patent Document 3, after a fine metal particle is formed by electrolytic plating and a blackened metal foil is bonded to a transparent substrate, a mesh pattern is formed by etching, and both surfaces of the metal layer pattern and By blackening the side surface, the light emitted from the display screen of the PDP is reflected by the surface of the shield material and returns to the display screen, the light transmittance of the shield material is lowered, and the visibility of the display screen is deteriorated. Is disclosed.

However, in the method of Patent Document 3, a fine uneven shape is formed on the surface of the adhesive layer that bonds the transparent substrate and the metal foil. This is because the fine uneven shape of the metal foil is transferred to the portion where the adhesive layer is exposed in the portion where the metal foil is dissolved and removed by etching, and the fine uneven shape is transferred as it is. Because it is.
For this reason, in the metal mesh pattern formed by etching the metal foil, it is inevitable that the haze value of the adhesive layer in the portion where the metal foil becomes a void by dissolving and removing by etching becomes high, and the transparent treatment In order to reduce the haze value by performing the above, it was necessary to fill the concave portions of the metal mesh pattern with a transparent resin and to further provide an antireflection layer.
As described above, the patterning of the metal layer by the metal foil etching method has a problem from the viewpoint of resource saving and manufacturing cost.

  The present invention has been made in view of the above circumstances, and uses an electromagnetic wave shielding material for display and an electromagnetic wave shielding material for display that can be manufactured at high productivity and low cost as a whole while being excellent in visibility. It is an object to provide an optical filter for display.

  In order to solve the above-mentioned problems, the present invention provides a method for producing a photographic material on one surface of a transparent substrate, a sheet-like substrate subjected to a release treatment is laminated via an adhesive layer, and on the other surface of the transparent substrate. A fine metal mesh pattern of developed silver generated by the method and a metal mesh pattern composed of a plating layer laminated thereon are formed, and the metal mesh pattern is a metal mesh pattern according to a screen size of a display, Provided an electromagnetic wave shielding material for a display, characterized in that the surface is blackened and the concave portion of the metal mesh pattern is not embedded with a resin for transparency treatment, and the metal mesh pattern is exposed to the outside air. To do.

  Further, in the present invention, a metal mesh pattern comprising a fine silver mesh pattern of developed silver produced by a photographic method and a plating layer laminated thereon is formed on at least one surface of a transparent substrate, and the metal mesh pattern Is a metal mesh pattern according to the screen size of the display, the surface of the plating layer is blackened, and the metal mesh pattern is not exposed in the concave portion of the metal mesh pattern without embedding a transparent resin. An electromagnetic wave shielding material for a display, which is characterized by being exposed to outside air.

It is preferable that a silver halide thin film mesh pattern is formed on the surface where the fine silver mesh pattern of developed silver produced by the photographic method is in contact with the transparent substrate.
An electrode frame is preferably disposed around the metal mesh pattern.

  Further, the fine silver mesh pattern of developed silver produced by the photographic method is one produced by a negative development method in which developed silver appears in the exposed part, or a positive type in which developed silver appears in the unexposed part. Any of those produced by the developing method described above is preferable.

  In addition, the present invention provides any of the above-described electromagnetic shielding materials for a display on the display side of a front glass plate in which a gap layer is disposed in front of the front panel of the display. Provided is an optical filter for display which is arranged to be

  Between the front glass plate and the electromagnetic wave shielding material for display, at least an ultraviolet absorbing layer and a near infrared absorbing layer are laminated, and on the viewing side of the front glass plate, one surface of the transparent substrate One or more functional layers selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer are formed, and an adhesive layer is laminated on the other surface of the transparent substrate. It is preferable that the functional film which becomes becomes bonded through the said adhesive layer.

  Further, in the present invention, the electromagnetic wave shielding material for display described above is bonded to the display side of the front glass plate disposed with a gap layer in front of the front panel of the display via an adhesive layer. An optical filter for display is provided.

  Further, on the surface of the front glass plate on which the electromagnetic wave shielding material for display is not bonded, a near infrared absorbing layer, an ultraviolet absorbing layer, a hard coat layer, an antistatic layer, an antireflection layer, an antifouling layer It is preferable that an optical functional film having one or more optical functional layers selected from the group consisting of be bonded via an adhesive layer.

  According to the present invention, the surface of the plated layer of the metal mesh pattern is blackened, and further, the silver halide thin film layer is formed on the surface where the fine silver mesh pattern of the developed silver produced by the photographic process is in contact with the transparent substrate. Therefore, the entire circumference of the fine line of the metal mesh pattern is blackened. For this reason, reflection of external light entering the viewing side can be prevented, and light emitted from the display screen of the display is reflected on the surface of the metal mesh pattern and reflected back to the display screen, thereby reducing the visibility of the display screen. Can be prevented.

In addition, according to the present invention, since there is no step of bonding a metal foil having fine irregularities to a transparent substrate, the adhesive layer of the transparent substrate to which the shape of the fine irregularities of the metal foil is transferred is a metal foil. Is not accompanied by the phenomenon that the metal mesh pattern is removed by etching, and the process of transparentizing the surface of the metal mesh pattern can be omitted. Furthermore, an antireflection layer can be omitted.
Therefore, it is possible to reduce the number of manufacturing steps and increase the yield, and to provide an electromagnetic shielding material for display that is manufactured at a high productivity and at low cost as a whole, and an optical filter for display using the electromagnetic shielding material for display. Can do.

The present invention will be described below with reference to the drawings based on the best mode.
FIG. 1 is a schematic cross-sectional view showing an example of the electromagnetic wave shielding material of the present invention. The electromagnetic wave shielding material 7 has a metal mesh pattern 6 formed on one surface of the transparent substrate 1. The metal mesh pattern 6 is not embedded with a resin for transparency treatment, and the metal mesh pattern 6 is exposed to the outside air.

FIG. 2 is a partial detailed sectional view of the metal mesh pattern 6 in the electromagnetic wave shielding material 7 shown in FIG. On one surface of the transparent substrate 1, a fine silver mesh pattern 3 of developed silver produced by a photographic method is formed, and a metal mesh pattern 6 made of a plating layer 4 laminated thereon is formed.
A silver halide thin film mesh pattern 2 is formed on the surface where the fine silver mesh pattern 3 of developed silver produced by the photographic method is in contact with the transparent substrate 1, and the surface of the plating layer 4 is blackened. A blackening treatment layer 5 is formed.
Therefore, the entire circumference of the fine line of the metal mesh pattern 6 is covered with the black coating (2 and 5).

FIG. 3 is a schematic plan view showing an example of the electromagnetic wave shielding material of the present invention. In this electromagnetic shielding material 7, a metal mesh pattern 6 corresponding to the screen size of the display is formed on the entire surface of the electromagnetic shielding material 7 on at least one surface of the transparent substrate.
FIG. 4 is a schematic plan view showing another example of the electromagnetic wave shielding material of the present invention. In this electromagnetic wave shielding material 9, a metal mesh pattern 6 corresponding to the screen size of the display is formed on at least one surface of the transparent substrate, and an electrode frame 8 is disposed around the metal mesh pattern 6.

  FIG. 5 is a schematic sectional view showing another example of the electromagnetic wave shielding material of the present invention. The electromagnetic shielding material 9 has a metal mesh pattern 6 corresponding to the screen size of the display formed on one surface of the transparent substrate 1, and an electrode frame 8 made of a metal mesh or a metal thin film is formed around the metal mesh pattern. Has been. The metal mesh pattern 6 is not embedded with the resin for the transparent treatment, and the metal mesh pattern 6 is exposed to the outside air. As shown in FIG. 2, the metal mesh pattern 6 in the electromagnetic wave shielding material 9 shown in FIG. 5 is formed with a fine silver mesh pattern 3 of developed silver produced by a photographic method on one surface of the transparent substrate 1, The metal mesh pattern 6 which consists of the plating layer 4 laminated | stacked on the top can be formed.

  FIG. 6 is a schematic cross-sectional view showing an example of an electromagnetic wave shielding material according to the prior art. In this electromagnetic wave shielding material 26, a metal mesh pattern 25 is formed by etching a copper foil bonded to the resin substrate 21 via the adhesive layer 22. In the portion 27 where the copper foil is dissolved and removed by etching, the adhesive layer 22 is exposed in a state where the unevenness of the copper foil is transferred to the adhesive layer. A concave portion of the metal mesh pattern 25 is filled with an adhesive layer 23 for a transparency treatment, and an antireflection layer 24 is provided thereon.

  7 and 8 are schematic cross-sectional views illustrating examples of the optical filter for display according to the present invention. The electromagnetic wave shielding material 9 is bonded to the display side of the front glass plate 11 via an adhesive layer 10. Here, the electromagnetic wave shielding material 9 exemplifies the one having the electrode frame 8 around the metal mesh pattern 6 in FIG. 5, but the electromagnetic wave shielding material 7 can be used without the electrode frame 8 in FIG. 1. .

  7 and 8, the metal mesh pattern 6 is such that the resin for transparency treatment is not embedded in the recess, and the metal mesh pattern 6 is the outermost surface in the display optical filter. It is arranged. Thereby, the metal mesh pattern 6 is exposed to the outside air. The front panel of the display is disposed on the display side (the side indicated by arrow D in FIG. 8) of the display optical filter with the gap layer therebetween.

7 and 8, the front glass plate 11 is disposed in front of the front panel (not shown) of the display with a gap layer therebetween, and the adhesive layer 10 is a metal of the transparent substrate 1. It is laminated on the surface where the mesh pattern 6 is not formed.
In the display optical filter of FIG. 7, the pressure-sensitive adhesive layer 10 is bonded to the near-infrared absorbing layer 13 disposed on the display side of the front glass plate 11. In the display optical filter of FIG. 8, the pressure-sensitive adhesive layer 10 is bonded to the display side of the front glass plate 11.

  In the optical filter for display shown in FIG. 7, at least an ultraviolet absorbing layer 14 and a near infrared absorbing layer 13 are laminated between the front glass plate 11 and the display electromagnetic wave shielding material 9, and further, the viewing side of the front glass plate 11. The functional film 17 is bonded to the surface (the side indicated by the arrow E in FIG. 7) via the pressure-sensitive adhesive layer 12.

  Further, the optical filter for display shown in FIG. 8 has an optical functional film 18 on the surface of the front glass plate 11 on which the electromagnetic wave shielding material is not bonded (viewing side) with the adhesive layer 12 interposed therebetween. It is made by bonding.

The near-infrared absorbing layer 13 is, for example, an NIR resin layer in which a near-infrared (NIR) absorbent is included in a transparent substrate. Ultraviolet rays are classified into three types, UVA (320 to 400 nm), UVB (290 to 320 nm), and UBC (280 to 290 nm), depending on the length of the wavelength.
The ultraviolet absorbing layer 14 is, for example, a UVA adhesive layer in which an ultraviolet (UVA) absorber is included in the adhesive.

  In the present invention, the functional film has one or more functional layers selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer. In the example shown in FIG. 7, the functional film 17 is one in which one or more functional layers 16 are formed on one surface of the transparent substrate 15 serving as the substrate, and the other surface of the transparent substrate 15. It is bonded to the viewing side of the front glass plate 11 through the pressure-sensitive adhesive layer 12 laminated on the front. For example, for example, an AR layer 16 in which an antireflection film is formed on a PET resin 15 can be used.

  In the present invention, the optical functional film has one or more optical functional layers selected from the group consisting of a near-infrared absorbing layer, an ultraviolet absorbing layer, a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer. . In the example shown in FIG. 8, the optical functional film 18 has a near-infrared absorbing layer 13 and an ultraviolet absorbing layer 14 laminated on one surface of a transparent substrate 15 serving as the substrate, and the other surface of the transparent substrate 15. Further, one or more functional layers 16 selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer are formed, and the pressure-sensitive adhesive layer 12 is laminated on the surface of the near infrared absorption layer 13. It is pasted through.

As shown in FIGS. 1 and 2, the electromagnetic wave shielding material for display according to the present invention is laminated on at least one surface of a transparent substrate 1 and a fine silver mesh pattern 3 of developed silver produced by a photographic method, and the fine silver mesh pattern 3 thereon. A metal mesh pattern 6 made of the plated layer 4 is formed.
The metal mesh pattern is a metal mesh pattern corresponding to the screen size of the display, and the surface of the plating layer 4 is blackened to form a blackened layer 5. Further, a thin silver halide film pattern surface 2 having a black color is formed on the surface where the fine silver mesh pattern 3 of developed silver produced by the photographic method is in contact with the transparent substrate 1.
It is preferable that the resin for transparentizing treatment is not embedded in the convex and concave portions of the metal mesh pattern, and the metal mesh pattern is exposed to the outside air.

The electromagnetic wave shielding material for display of the present invention may be composed of only the metal mesh pattern 6 as shown in FIGS. 1 and 3, or alternatively, the metal mesh pattern 6 and the metal mesh pattern 6 as shown in FIGS. The electrode frame 8 may be arranged around the metal mesh pattern 6.
The line width of the electrode frame 8 is about 5 to 20 mm, and is wider than, for example, the thin line width of a metal mesh pattern made of thin lines with a line width of about 10 to 100 μm.

As shown in FIGS. 3 and 4, the metal mesh pattern 6 is formed with respect to the display screen and the electrode frame 8 so as to have an optimum bias angle (θ) corresponding to the resolution of the display panel. Is preferred.
In the present specification, the bias angle of the metal mesh pattern formed on the electromagnetic shielding material refers to the optimum bias angle of the metal mesh pattern with respect to the electrode frame provided.
In order to prevent the moire phenomenon caused by the interference of the metal mesh pattern with the black stripe pattern of the display, it is necessary to form the metal mesh pattern so as to obtain an optimum bias angle according to the resolution of the display panel.

  The metal mesh pattern 6 preferably has a fine silver mesh pattern 3 of developed silver produced by a photographic method and a plating layer 4 laminated thereon by electroless plating and / or electrolytic plating.

In the silver halide fine line mesh pattern formed by exposure and development by the photographic process, the surface in contact with the transparent substrate is not completely reduced, and a part of the black fine line mesh pattern made of silver halide as it is It remains as 2.
Also, a plating layer 4 is laminated on the metallic silver fine wire mesh pattern 3 by the reduction reaction, and the surface of the plating layer 4 is subjected to blackening treatment to form a blackening treatment layer 5.

Therefore, the electromagnetic wave shielding material for display according to the present invention is formed with a fine silver mesh pattern of developed silver produced by a photographic method and a metal mesh pattern composed of a plating layer laminated thereon on at least one surface of a transparent substrate. The metal mesh pattern is a metal mesh pattern corresponding to the screen size of the display, and the surface of the plating layer is blackened. Further, a silver halide thin film pattern surface 2 is formed on the surface of the developed silver fine-line mesh pattern 3 generated by the photographic method in contact with the transparent substrate 1. Therefore, the entire periphery of the fine line of the metal mesh pattern is blackened to give a black color.
Further, in the electromagnetic wave shielding material for a display according to the present invention, the metal mesh pattern is exposed and exposed to the outside air because the resin for transparency treatment is not embedded in the concave portion of the metal mesh pattern.

(Metal mesh pattern manufacturing method)
The electromagnetic wave shielding material of the present invention forms a fine silver mesh pattern of developed silver that is exposed and developed using an exposure mask by a photographic method on one surface of a transparent substrate, and a metal plating is laminated thereon. It will be.
Hereinafter, a developed silver fine line mesh pattern produced by a photographic method, and a method for producing a metal mesh pattern by laminating metal plating on the developed silver fine line mesh pattern will be described.

In the present invention, either one of two different silver salt photographic development methods (positive photographic method and negative photographic method) may be used as a method for producing a fine line pattern comprising a metal layer used as an electromagnetic wave shielding material in the present invention. . Basically, a silver halide black mesh pattern formed by exposure / development by a photographic process is converted into a metal silver fine line mesh pattern by a reduction reaction.
Hereinafter, in order to avoid duplication of explanation, a method for producing a metal mesh pattern that can be used as an electromagnetic shielding material based on a positive photographic method will be described.

(Transparent substrate)
The transparent substrate 1 used in the present invention is preferably one having transparency in the visible region and generally having a total light transmittance of 90% or more. Especially, the resin film which has flexibility is used suitably at the point which is easy to handle. Specific examples of the transparent resin film used for the transparent substrate 1 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, Single-layer film having a thickness of 50 to 300 μm made of acetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, or the like A composite film having a plurality of layers made of a resin is exemplified.

(Formation of fine line pattern on transparent substrate)
A method for producing a metal mesh pattern comprising a fine silver mesh pattern of developed silver produced by a photographic process applicable to the present invention and a plating layer laminated thereon is made of metal silver developed by a positive photographic process. After the formation, a metal layer composed of a metal plating layer is stacked thereon.

In the present invention, a fine-line mesh pattern of developed silver is generated on one surface of the transparent substrate by using a positive photographic method in which developed silver appears on a portion that is not exposed.
The base material provided with a layer containing a substance that deposits metallic silver by exposure and development on one side of the transparent base material is exposed using a previously prepared exposure mask, and then developed, thereby developing silver. Generate a fine line pattern consisting of layers.

Hereinafter, development of a fine line pattern made of developed silver by developing a positive photographic method (DTR method) in which developed silver appears in a non-exposed portion, and developing silver by a positive photographic method (DTR method) in which developed silver appears in an unexposed portion. A method for producing a fine line pattern made of a metal layer having a plating layer formed thereon will be described.
In the case of the DTR method, it is preferable that a physical development nucleus layer is provided in advance on the transparent substrate surface. In order to develop developed silver by exposure and development using the DTR method on both sides of the transparent substrate as in the present invention, after forming a physical development layer on one side, a physical development nucleus is formed on the other side. A layer may be provided to develop developed silver by exposure and development.

  As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The fine particle layer of these physical development nuclei can be provided on the transparent substrate by a vacuum deposition method, a cathode sputtering method, a coating method or the like. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per square meter in solid content.

  The transparent substrate can be provided with an adhesive layer of a polymer latex layer such as vinylidene chloride or polyurethane, and an intermediate layer made of a hydrophilic binder such as gelatin can be provided between the adhesive layer and the physical development nucleus layer. it can.

  The physical development nucleus layer preferably contains a hydrophilic binder. The amount of the hydrophilic binder is preferably about 10 to 300% by mass with respect to the physical development nucleus. As the hydrophilic binder, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used. The physical development nucleus layer may also contain a hydrophilic binder crosslinking agent.

  The physical development nucleus layer and the intermediate layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like. In the present invention, the physical development nucleus layer is preferably provided as a continuous and uniform layer by the above-described coating method.

  The supply of silver halide for depositing metallic silver on the physical development nucleus layer is performed by a method in which the physical development nucleus layer and the silver halide emulsion layer are integrally formed in this order on a transparent substrate, or another paper or plastic resin. There is a method of supplying a soluble silver complex salt from a silver halide emulsion layer provided on a substrate such as a film. From the viewpoint of cost and production efficiency, the former physical development nucleus layer and the silver halide emulsion layer are preferably provided integrally.

The silver halide emulsion can be produced according to a general method for producing a silver halide emulsion of a silver halide photographic light-sensitive material. The silver halide emulsion is usually prepared by mixing and ripening an aqueous silver nitrate solution, an aqueous halogen solution of sodium chloride or sodium bromide in the presence of gelatin.
The silver halide composition of the silver halide emulsion layer preferably contains 80 mol% or more of silver chloride, and more preferably 90 mol% or more is silver chloride. The conductivity of the physically developed silver formed by increasing the silver chloride content is improved.

(Exposure method)
When an electromagnetic wave shielding material is produced using a photosensitive material in which a silver halide emulsion layer is coated directly on the physical development nucleus layer or via an intermediate layer, it is usually an arbitrary one such as a mesh pattern. An exposure mask with a fine line pattern and the photosensitive material are in close contact with each other, or a digital image with an arbitrary fine line pattern is scanned and exposed to the photosensitive material with various laser beam output machines.

  The silver halide emulsion layer is sensitive to various light sources. As one method for producing an electromagnetic wave shielding material, for example, formation of physically developed silver having a fine line pattern such as a mesh shape can be mentioned. In this case, the silver halide emulsion layer is exposed in a fine line pattern. As an exposure method, a method of exposing a fine line pattern transmission original and a silver halide emulsion layer in close contact with each other, or scanning exposure using various laser beams. There are ways to do this. The former contact exposure is possible even if the silver halide has relatively low photosensitivity, but in the case of scanning exposure using laser light, relatively high photosensitivity is required.

  Therefore, when the latter exposure method is used, the silver halide may be subjected to chemical sensitization or spectral sensitization with a sensitizing dye in order to increase the sensitivity of the silver halide. Chemical sensitization includes metal sensitization using a gold compound or silver compound, sulfur sensitization using a sulfur compound, or a combination thereof. Gold-sulfur sensitization using a gold compound and a sulfur compound in combination is preferable. In the above-described method of exposing with laser light, a laser beam having an oscillation wavelength of 450 nm or less, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm is used. It can be handled even under a yellow fluorescent lamp.

(Exposure equipment)
As an exposure apparatus using the above exposure method, there are a single wafer processing type exposure apparatus using a single wafer type exposure mask (photomask) and a continuous exposure apparatus capable of forming a continuous fine line pattern. A single-wafer processing type exposure apparatus uses a single-wafer exposure mask (photomask) on which a predetermined mask pattern is formed, and a transparent layer provided with a layer containing a substance that deposits metallic silver by transparent exposure and development. The roll sheet fed from the base fabric roll of the base material is intermittently fed to the exposure apparatus, the inside of the apparatus is evacuated, the exposure mask and the base material are brought into close contact with each other, and then exposed to, for example, ultraviolet rays. . In a single wafer processing type exposure apparatus, vacuum exhaust, exposure, and release to the atmosphere are intermittently performed, so that the processing speed is slow and a seamless continuous pattern cannot be obtained.

  On the other hand, a continuous exposure apparatus capable of continuously forming a fine line pattern can also be used. That is, the roll sheet drawn out from the raw roll body of the transparent substrate provided with a layer containing a substance that deposits metallic silver by exposure and development is exposed using a continuous exposure apparatus, and then developed, A fine line pattern made of developed silver is generated at regular intervals in the longitudinal direction of the transparent substrate.

  The continuous exposure apparatus is, for example, a cylindrical drum made of a material that transmits light used for exposure in a photographic process, an exposure mask portion provided on the outer peripheral wall of the cylindrical drum, and an exposure mask disposed in the cylindrical drum. And a device for exposing a transparent substrate wound around the cylindrical drum by light emitted from the light source inside the cylindrical drum. In this continuous exposure apparatus, a light source cover having an opening that transmits light in a specific irradiation direction can be provided around the light source for exposure. The pattern for exposing the transparent substrate is determined by the pattern of the portion that transmits light in the exposure mask portion. The exposure mask portion is disposed on the cylindrical drum by, for example, being provided on the surface (inner surface or outer surface) of the outer peripheral wall of the cylindrical drum, or being inserted or sandwiched inside the outer peripheral wall.

  In this continuous exposure apparatus, since the cylindrical drum rotates at the same speed as the transparent substrate that is continuously transferred, the transparent drum is transparent while the portions of the transparent substrate are exposed at the portions wound around the cylindrical drum. It is possible to continue the exposure for the required time without shifting the pattern of the exposure mask portion with respect to the base material (the pattern of the light transmitting portion and the light shielding portion). The light source used in the exposure apparatus can be appropriately selected depending on the spectral characteristics and sensitivity of the silver halide emulsion contained in the silver halide emulsion layer. For example, a tungsten lamp, an ultraviolet lamp, a fluorescent lamp, a xenon lamp, etc. are used. can do.

At the time of exposure, the light source cover does not rotate, and the opening portion is always directed in a certain direction, so that light from the light source is blocked by the light source cover at a portion where the transparent substrate is away from the surface of the cylindrical drum. That is, the exposure of the transparent base material by the light source of the exposure apparatus is performed within a certain range in which the transparent base material is wound around the surface of the cylindrical drum on the transfer path, so that the control of the light amount and time of exposure is ensured. Can be done.
The continuous exposure apparatus has an advantage that the processing speed is higher than that of a conventional single wafer processing type exposure apparatus and a continuous pattern having no joints can be obtained.

(Development method)
Halation at any position on the transparent substrate on which the physical development nucleus layer is provided, for example, an adhesive layer, an intermediate layer, a physical development nucleus layer or a silver halide emulsion layer, a protective layer, or a backing layer provided with a support interposed therebetween Or a dye or pigment for preventing irradiation may be contained.

  When producing an electromagnetic shielding material using a photosensitive material in which a silver halide emulsion layer is coated directly on the physical development nucleus layer or via an intermediate layer, an arbitrary fine line pattern such as a mesh pattern is used. After exposing a transparent original and the photosensitive material in close contact, or by scanning and exposing a digital image of an arbitrary fine line pattern onto the photosensitive material with various laser light output machines, in the presence of a soluble silver complex salt forming agent and a reducing agent. Silver complex diffusion transfer development (DTR development) occurs by processing in an alkaline solution, and the silver halide in the unexposed area is dissolved to form a silver complex salt, which is reduced on the physical development nuclei to precipitate metallic silver, resulting in a fine line. A physically developed silver thin film with a pattern can be obtained. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After development, the silver halide emulsion layer and the intermediate layer, or the protective layer provided as necessary, are washed away with water, and a physically developed silver thin film having a fine line pattern is exposed on the surface.

  After DTR development, the silver halide emulsion layer or the like provided on the physical development nucleus layer may be removed by washing with water or transferring and peeling to a release paper or the like. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like.

  On the other hand, when the soluble silver complex salt is supplied from a silver halide emulsion layer provided on a substrate different from the transparent substrate on which the physical development nucleus layer is coated, the silver halide emulsion layer is exposed as described above. After that, a transparent substrate coated with a physical development nucleus layer and another photosensitive material coated with a silver halide emulsion layer are superposed in an alkaline solution in the presence of a soluble silver complexing agent and a reducing agent. After several tens of seconds to several minutes after taking out from the alkaline solution, the both are removed to obtain a physically developed silver thin film having a fine line pattern deposited on the physical development nuclei.

  Next, a soluble silver complex salt forming agent, a reducing agent, and an alkali solution necessary for silver complex diffusion transfer development will be described. The soluble silver complex forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound that reduces this soluble silver complex salt to precipitate metallic silver on physical development nuclei. These actions are performed in an alkaline solution.

  Examples of the soluble silver complex forming agent used in the present invention include sodium thiosulfate, thiosulfate such as ammonium thiosulfate, thiocyanate such as sodium thiocyanate and ammonium thiocyanate, alkanolamine, sodium sulfite, and potassium bisulfite. Sulfites such as T. H. Examples include the compounds described in 474-475 (1977) of James The Theory of the Photographic Process 4th edition.

  As the reducing agent, a developing agent known in the field of photographic development can be used. For example, hydroquinone, catechol, pyrogallol, methylhydroquinone, polyhydroxybenzenes such as chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl- Examples include 3-pyrazolidones such as 4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like.

  The above-mentioned soluble silver complex salt forming agent and reducing agent may be applied to the transparent substrate together with the physical development nucleus layer, added to the silver halide emulsion layer, or contained in the alkaline solution. It may be allowed to be contained, and may be further contained in a plurality of positions, but is preferably contained at least in the alkaline liquid.

  The content of the soluble silver complex salt forming agent in the alkaline solution is suitably used in the range of 0.1 to 5 mol per liter of the developer, and the reducing agent is 0.05 to 1 per liter of the developer. It is suitable to use in the molar range.

  The pH of the alkaline solution is preferably 10 or more, and more preferably in the range of 11-14. Application of the alkaline solution for silver complex diffusion transfer development may be an immersion method or a coating method. The immersion method is, for example, transporting while immersing a transparent substrate provided with a physical development nucleus layer and a silver halide emulsion layer in an alkaline solution stored in a large amount in a tank. For example, about 40 to 120 ml of an alkaline solution per square meter is applied on the silver halide emulsion layer.

(Thin wire mesh pattern with developed silver)
As described above, as the fine line mesh pattern, for example, there are fine lines having a line width of about 10 to 100 μm provided in a lattice shape vertically and horizontally, but if the fine line width is reduced and the interval between the lattices is increased, the translucency is However, the conductivity decreases, and conversely, if the width of the fine line is increased and the interval between the lattices is decreased, the translucency is decreased and the conductivity is increased.
With only a silver image obtained by physical development of an arbitrary fine line pattern formed on one surface of a transparent substrate according to the present invention, translucency with a total light transmittance of 50% or more and conductivity with a surface resistivity of 10 ohms / square or less. It is difficult to satisfy the sex at the same time.

  However, in the present invention, it is possible to reduce the surface resistivity to 10 ohms / □ or less by laminating a metal plating layer on a fine line mesh pattern made of developed silver on one surface of a transparent substrate. Become. For this reason, the positive photographic manufacturing method of the present invention can satisfy the translucency with a total light transmittance of 50% or more.

By the way, the silver image by the physical development itself forms a silver image because the metallic silver particles forming the silver image obtained after the development processing are extremely small and the amount of the hydrophilic binder present in the silver image is extremely small. A silver image is formed in a state where the metallic silver particles to be close to the close-packed state have electrical conductivity.
For this reason, it is possible to further improve electromagnetic wave shielding performance by performing electroless plating or electrolytic plating with a metal such as copper or nickel on the silver image.
In order to improve the total light transmittance of the fine line pattern from the metal layer, it is necessary to sufficiently increase the area of the light transmission portion between the fine lines with respect to the area of the region where the fine lines are provided. For this reason, it is preferable that the space | interval of a thin wire | line is 100-900 micrometers, More preferably, it is 150-700 micrometers.

(Plating on fine silver mesh pattern of developed silver)
The thickness of the plating layer laminated on the fine silver mesh pattern of developed silver can be arbitrarily changed depending on desired properties, but is in the range of 0.05 to 80 μm, preferably 0.2 to 30 μm.
When the electromagnetic wave shielding material of the present invention is used as an electromagnetic wave shielding material for an optical filter for display, when the metal mesh pattern has a fine line width of 15 to 80 μm, a thickness of 0.2 to 30 μm, and a pitch of 200 to 300 μm, It has excellent light transmission performance and electrical conductivity with light transmittance of 50% or more and surface resistivity of 1 ohm / □ or less, and exhibits a shielding effect of 30 dB or more over a wide frequency band such as 30 MHz to 1,000 MHz. can do.

  The metal plating applied on the fine silver mesh pattern of developed silver can be any of electroless plating, electrolytic plating, or a combination of both.

(Plating method)
In the present invention, a method for forming a metal plating layer laminated on a fine silver mesh pattern of developed silver produced by a photographic method is as follows.
A fine line mesh pattern made of developed silver produced by a photographic process is formed on one surface of the transparent substrate, and copper (Cu) and / or nickel (Ni) is plated on the fine line pattern.

In the present invention, the metal plating method can be performed by a known method. For example, the electrolytic plating method is a conventionally known method such as copper, nickel, silver, gold, solder, or a multilayer or composite system of copper / nickel. For these, reference can be made to documents such as “Surface Treatment Technology Overview; Technical Data Center, Inc., December 21, 1987, first edition, pages 281 to 422”.
It is preferable to use copper and / or nickel for reasons such as easy plating, excellent electrical conductivity, plating on a thick film, and low cost.

(Electroless copper plating)
The electroless copper plating solution preferably has a metal copper (Cu) concentration of 0.5 to 10 g / liter, more preferably 2 to 3 g / liter.
As temperature of a plating process liquid, 30-80 degreeC is preferable, More preferably, it is 40-50 degreeC. If the temperature of the plating solution is lower than 30 ° C., the copper deposition rate is slow, and if it is 80 ° C. or higher, the energy cost increases, which is not preferable.
The plating thickness is preferably 0.01 to 1 μm, and more preferably 0.05 to 0.2 μm. Further, the electroless copper plating solution may be any solution as long as it is a known plating solution.

(Electrolytic copper plating)
In the case of electrolytic copper plating, any plating solution such as copper sulfate, copper cyanide, and copper pyrophosphate may be used, but copper sulfate is preferable from the viewpoint of cost. In these electrolytic copper plating solutions, the concentration of copper (Cu) may be set to an appropriate concentration.
When using a copper sulfate plating bath, the sulfuric acid concentration is preferably 20 to 400 g / liter, more preferably 70 to 300 g / liter. If the sulfuric acid concentration is lower than 20 g / liter, the plating solution becomes unstable, and if it is higher than 300 g / liter, abnormalities occur in the plating particles.

The plating temperature is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. If the temperature of the plating solution is lower than 10 ° C., the plating time is increased and the cost is increased, and if it is higher than 60 ° C., the plating appearance is deteriorated.
The current density of electrolytic plating is preferably 0.05 to 20 A / cm ² , more preferably 0.5 to 8 A / cm ² . When the current density of electrolytic plating is lower than 0.05 A / cm ² , the plating time becomes longer and the cost increases. Moreover, when the current density of electrolytic plating is higher than 20 A / cm < ² >, since the external appearance of a plating film will worsen, it is unpreferable.

(Electrolytic nickel plating)
When performing electrolytic nickel plating, any plating bath such as watt bath (nickel sulfate, nickel chloride, boric acid), nickel sulfamate bath (nickel sulfamate, nickel chloride, boric acid), etc. But you can.

(Blackening treatment)
The outermost surface of the developed silver layer or metal plating layer is preferably blackened to prevent reflection of light due to the gloss of the metal.
When a fine line pattern made of developed silver by a positive photographic method is used as an electromagnetic shielding material, the DTR method is used to suppress the reflection of light from the display on the surface of the fine line pattern made of a metal layer and increase the contrast of the display screen. It is necessary to blacken the surface of the metallic silver layer formed by the above.

  In the DTR method, after exposure to an arbitrary fine line pattern, silver complex diffusion transfer development (DTR development) occurs by processing in an alkaline solution in the presence of a soluble silver complex salt forming agent and a reducing agent. The silver halide is dissolved to form a silver complex salt, which is reduced on the physical development nuclei to deposit metallic silver to obtain a physically developed silver thin film having a fine line pattern. The exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After the development, the silver halide emulsion layer and the intermediate layer, or the protective layer provided as necessary, are removed by washing, and the metal silver layer having a fine line pattern is exposed on the surface. This metal silver layer is again subjected to a halogenation treatment to obtain a blackened silver black.

In addition, when a fine-line mesh pattern of a metal layer composed of a developed silver layer produced by a positive type photographic method and a metal plating layer laminated thereon is used as an electromagnetic wave shielding material, light from the display is composed of a metal layer. In order to suppress reflection on the surface of the fine line mesh pattern and increase the contrast of the display screen, it is necessary to blacken the outermost surface of the plating layer.
As a method of blackening treatment on the surface of nickel plating, there is no particular limitation on the type of blackening treatment film and the composition of the blackening treatment liquid to be used. As a preferable example, when black nickel is used, sulfuric acid of the blackening treatment liquid is used. The concentration is preferably 10 to 50 g / liter, and more preferably 20 to 40 g / liter. When the concentration of nickel sulfate is lower than 10 g / liter, plating deposition is delayed and the cost is increased, and when it is higher than 50 g / liter, the finished color of the blackening treatment is not stable.

(Released release film)
In the electromagnetic wave shielding material of the present invention, a peeled sheet-like substrate is laminated on one surface (for example, the lower surface of FIGS. 1 and 5) of the transparent substrate via an adhesive layer (not shown). .
As the sheet-like base material used in the present invention, paper such as fine paper, glassine paper, coated paper, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyphenylene sulfide (PPS), polyethylene And synthetic resins such as polyolefin resins such as polypropylene, polyvinyl chloride resins, polyurethane resins, acrylic resins, and fluorine resins, but synthetic resins are preferably used because of easy handling.

The thickness of the sheet-like base material is not particularly limited, and a foamed base material can be used, and a multilayer structure obtained by laminating a plurality of sheet-like base materials can also be used. Furthermore, the sheet-like substrate may be colored, or a coat layer may be laminated for imparting functionality.
One side of the sheet-like substrate used in the present invention is subjected to a peeling treatment. As a peeling treatment method, a known method such as applying a silicone compound, a fluorine-based compound, a long-chain alkyl-based compound or the like to one side of a sheet-like substrate can be used.

(Adhesive layer)
In the electromagnetic wave shielding material of the present invention, an easily peeled sheet-like substrate is laminated on one surface of the transparent substrate via an adhesive layer.
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited as long as it is transparent in the visible region (that is, has sufficient transmittance), and is not limited to thermosetting resin, ultraviolet curable resin, or electron beam curable resin. It may be a curable resin such as a thermoplastic resin. From the viewpoint of transparency, an acrylic resin is preferably used.

Examples of the ultraviolet curable resin used include photopolymerizable prepolymers and / or monomers, and other monofunctional or polyfunctional monomers, various polymers, and photopolymerization initiators (acetophenones, benzophenones) as necessary. , Michler's ketone, benzyl, benzoin, benzoin ether, benzyl ketals, thioxanthones, etc.) and a sensitizer (amines, diethylaminoethyl methacrylate, etc.). Here, examples of the photopolymerizable prepolymer include polyester acrylate, polyester urethane acrylate, epoxy acrylate, and polyol acrylate.
Examples of the photopolymerizable monomer include monofunctional acrylates, bifunctional acrylates, and trifunctional or higher acrylates.
In addition to the above, phosphazene resins are also suitably used as the photopolymerizable prepolymer or monomer.

As the thermosetting resin and the electron beam curable resin, the same ultraviolet curable resin as described above is used. However, the electron beam curable resin does not require the addition of a polymerization initiator.
Appropriately selected transparent adhesive resin composition is applied on a transparent substrate that forms an electromagnetic shielding material for display by a known coating method such as a bar coating method, a roll coating method, or a gravure reverse coating method. After forming the pressure-sensitive adhesive layer, the sheet-like base material that has been subjected to the peeling treatment is bonded.

  Thus, in the electromagnetic wave shielding materials 7 and 9 for display of the present invention, an adhesive layer is formed in advance on the opposite side of the transparent substrate 1 from the side on which the metal mesh pattern 6 is formed, and the adhesive layer For example, when manufacturing the display optical filter of FIGS. 7 and 8, the electromagnetic wave shielding material is used as an adhesive. When bonding to the display side of the front glass plate 11 or the near-infrared absorbing layer 13 through the layer 10, the front glass plate through the pressure-sensitive adhesive layer 10 is peeled off and exposed. 11 can be bonded to the display side or near-infrared absorbing layer 13, which facilitates the manufacturing process.

(Lamination of functional film)
The “functional film” required for the optical filter for display of the present invention is formed by laminating one or more functional layers selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer and an antifouling layer. Can be produced. The functional film may have a plurality of functional layers according to the required functional level.
In the optical filter for display shown in FIG. 7, at least an ultraviolet absorbing layer 14 and a near infrared absorbing layer 13 are laminated between the front glass plate 11 and the display electromagnetic wave shielding material 9, and further, on the viewing side of the front glass plate 11. The functional film 17 described above is bonded to the surface via the pressure-sensitive adhesive layer 12.

(Lamination of optical functional film)
The “optical functional film” required for the optical filter for display of the present invention is selected from the group consisting of a near-infrared absorbing layer, an ultraviolet absorbing layer, a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer. Further, it can be produced by laminating one or more optical functional layers. The optical functional film can have a plurality of optical functional layers according to the required functional level. For example, the optical functional film is composed of one or more functional layers selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer, a near infrared absorbing layer, and an ultraviolet absorbing layer. It can also have at least 3 types of optical function layers.
In the optical filter for display shown in FIG. 8, the above-mentioned optical functional film 18 has the adhesive layer 12 on the surface of the front glass plate 11 on the side where the electromagnetic wave shielding material 9 is not bonded (that is, the viewing side). It is pasted through.

(Near-infrared absorbing layer)
The near-infrared absorbing layer of the present invention can be, for example, a transparent resin layer in which a near-infrared (NIR) absorbing dye is dispersed.
The function of the transparent resin layer (hereinafter referred to as the NIR resin layer) in which the near-infrared absorbing dye is dispersed is to reduce the near-infrared transmittance in the wavelength region of 850 to 1100 nm to 15% or less, preferably 10% or less. It is desirable to be.

  Specific examples of near-infrared absorbing dyes include immonium salt compounds, diimmonium salt compounds, aminium salt compounds, nitroso compounds and their metal complexes, cyanine compounds, squarylium compounds, thiol nickel complex compounds, aminothiol nickel compounds Complex salt compounds, phthalocyanine compounds, naphthalocyanine compounds, triarylmethane compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, carbon black, antimony oxide, tin oxide doped with indium oxide, Group 4 of the periodic table, Examples thereof include oxides, carbides or borides of metals belonging to Group 5 or Group 6.

The near-infrared absorbing dye is composed of two or more kinds of dyes, a long-wavelength near-infrared absorbing dye and a short-wavelength near-infrared absorbing dye, each having absorption ability in different wavelength bands in the absorption wavelength band of 850 nm to 1100 nm. It is preferable.
The long-wavelength near-infrared absorbing dye is one selected from diimonium salt compounds, and the short-wavelength near-infrared absorbing dye is a phthalocyanine compound, a cyanine compound, or a thiol nickel complex compound. It is preferable that it is 1 type, or 2 or more types of pigment | dyes selected from these.

The NIR resin layer can be formed by dispersing a near-infrared absorbing dye in a binder made of a transparent resin.
The glass transition temperature (Tg) of the binder resin is preferably 80 to 160 ° C. As a result, the weather resistance of the binder resin itself is improved, the near infrared absorbing performance of the near infrared absorbing coating film is maintained, and the weather resistance and physical properties of the near infrared absorbing coating film itself are further improved. Become. Preferably, it is -50-130 degreeC, More preferably, it is 20-110 degreeC, More preferably, it is 40-100 degreeC.

  Examples of the binder resin include (meth) acrylic resin, (meth) acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, melamine resin, urethane resin, styrene resin, and alkyd resin. Modification of resins, phenolic resins, epoxy resins, polyester resins, (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone resins, silicone alkyd resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc. Examples include fluororesins such as silicone resins, polyvinylidene fluoride, and fluoroolefin vinyl ether polymers. Thermoplastic resins may be used, and thermosetting resins, moisture curable resins, UV curable resins, electron beam curable resins, etc. Resin may be used

  Also, organic binder resins such as synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber or natural rubber; silica sol, alkali silicate, silicon alkoxide and their (hydrolysis) Conventionally known binder resins such as inorganic binders such as condensates and phosphates may be mentioned. These may be used alone or in combination of two or more.

  Among these, (meth) acrylic resins, (meth) acrylic urethane resins, (meth) acrylic silicone resins, polyesters can be dried at a relatively low temperature to form a near-infrared absorbing coating film. It is preferably a fluorine-based resin such as a modified resin such as a vinyl resin, a silicone resin, a silicone alkyd resin, a silicone urethane resin, a silicone polyester resin, or a silicone acrylic resin, a polyvinylidene fluoride, or a fluoroolefin vinyl ether polymer. Note that acrylic resins and methacrylic resins are also referred to as acrylic resins.

  When forming the NIR resin layer, as a compound other than those described above, for example, one or two or more solvents, additives, and the like may be included. Such a solvent is not particularly limited, and examples thereof include aromatic solvents such as toluene and xylene; alcohol solvents such as isopropyl alcohol, n-butyl alcohol, propylene glycol methyl ether, and dipropylene glycol methyl ether; butyl acetate. Ester solvents such as ethyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; one or more organic solvents such as dimethylformamide.

  In addition, as the additive, a conventionally known additive generally used in a resin composition for forming a film, a coating film, or the like can be used. For example, a leveling agent; inorganic fine particles such as colloidal silica and alumina sol; Antifoaming agent, anti-sagging agent, silane coupling agent, viscosity modifier, metal deactivator, peroxide decomposer, plasticizer, lubricant, rust preventive agent, organic and inorganic UV absorber, inorganic System heat ray absorbent, organic / inorganic flameproofing agent, antistatic agent and the like.

In order to improve the durability of the dye, a quencher or an antioxidant can be added.
Examples of such quenchers include metal complex materials, such as “MIR101” manufactured by Midori Chemical Co., “EST5” manufactured by Sumitomo Seika Co., Ltd., and the like.
Representative antioxidants include hindered amine compounds, hindered phenol compounds, phosphite compounds, and the like, and these can be used alone or in combination of two or more.

Examples of methods for applying the NIR resin layer include immersion, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, blade coating, bar coating, reverse coating, die coating, spray coating, electrostatic coating, and the like. The method is mentioned. In these cases, the organic solvent described above can be appropriately mixed and applied to the near-infrared absorbing resin composition.
The thickness of the near infrared absorber layer is not particularly limited as long as it is appropriately set depending on the intended use. For example, the thickness upon drying is 1 to 50 μm, preferably 1 to 20 μm.

(UV absorbing layer)
The ultraviolet absorbing layer is provided closer to the visual side than the near infrared absorbing layer in order to prevent the near infrared absorbing layer from being deteriorated by external light. If necessary, one or more ultraviolet absorbing layers can be provided at an appropriate position of the optical filter.
As a method for forming the ultraviolet absorbing layer, a method of mixing an ultraviolet absorber in a transparent substrate, a transparent resin layer, or an adhesive layer, a coating solution containing the ultraviolet absorber is directly or otherwise applied to the transparent substrate. The method of apply | coating through the layer of this is mentioned.

  As the ultraviolet absorber, both an organic ultraviolet absorber and an inorganic ultraviolet absorber can be used, but those having a wavelength at 50% transmittance of 350 to 420 nm are preferable, and 360 nm to 400 nm are more preferable. . An ultraviolet absorber having a wavelength of 50% transmittance and a wavelength lower than 350 nm is not preferable because the ultraviolet blocking ability is weak, and an ultraviolet absorber having a wavelength higher than 420 nm is strongly colored.

  Examples of organic ultraviolet absorbers include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc., phenyl salicylate, 4-t-butylphenyl salicylate, 2, Hydroxybenzoate systems such as 5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate Compounds and the like. Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate. These ultraviolet absorbers can be used alone or in combination of two or more.

(Antireflection layer)
Here, the antireflection layer is for preventing reflection of visible light from the outside of the optical filter, and in the case of a single layer, a substance having a lower refractive index than a transparent substrate, for example, a polysiloxane structure A thin film made of fluorine-containing organic compound, MgF ₂ , SiO ₂ or the like is formed.
The film thickness of the antireflection layer is such that the optical film thickness d (nm) is set to d = λ / 4 (where λ is a design wavelength of 500 to 580 nm) to form a single antireflection layer.
In the case of multi-layers, a material having a higher refractive index than that of a transparent substrate, for example, a thin film such as titanium oxide, zirconium oxide or ITO, and a material having a lower refractive index than that of a transparent substrate, such as a thin film of silicon oxide Are stacked alternately.
The formation method of such a metal oxide thin film is not specifically limited, It can carry out using well-known methods, such as sputtering method, a vacuum evaporation method, and a wet coating method.

(Hard coat layer)
Abrasion resistance and scratch resistance can be imparted by applying the resin composition for the hard coat layer directly or through another layer to the transparent base film by a known method.
The hard coat layer can be formed by applying, drying, and curing a liquid obtained by dissolving a hard coat agent in a solvent as necessary.
The hard coat agent is not particularly limited, and various known hard coat agents such as a thermosetting hard coat agent and an ultraviolet curable hard coat agent can be used.
As the thermosetting hard coat agent, for example, a silicone resin-based, acrylic resin-based, melamine resin-based hard coat agent, or the like can be used. Silicone resin hard coating agents are superior in hardness, weather resistance, and scratch resistance compared to conventional acrylic resin hard coating agents.

In addition, as ultraviolet curable hard coating agents, hard coating agents such as radically polymerizable hard coating agents such as unsaturated polyester resins and acrylic resins, and cationic polymerizable hard coating agents such as epoxy resins and vinyl ether resins are used. Can be used.
In the case of an ultraviolet curable hard coat agent, it is cured by irradiation with ultraviolet rays. For ultraviolet irradiation, a lamp such as a xenon lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp can be used.
The hard coat layer may further contain various additives such as an antioxidant, an antistatic agent and a flame retardant as required. Various additives can be added and applied to the hard coat agent.
By setting the thickness of the hard coat layer to 0.05 to 5 μm, preferably about 0.5 to 3 μm, the antireflection film can be provided with wear resistance and scratch resistance.

(Anti-fouling layer)
When coating an antifouling layer on the antireflection layer as the outermost layer, after applying a fluorine or silicone antifouling coating agent to the surface of the antireflection layer, the antifouling layer can be wiped off. Can be formed.
The antifouling layer protects the antireflection layer and enhances the antifouling performance.
As the antifouling coating agent, a fluorine resin or a silicone resin can be used. For example, in the case where the low refractive index layer of the antireflection layer was formed by SiO _2, the fluorosilicate water-repellent paints such as fluoroalkyl silane is preferably used.
The antifouling layer can be formed by applying an antifouling coating agent diluted with a solvent by screen printing, a micro gravure coater or the like.

The thickness of the antifouling layer must be set so as not to hinder the function of the antireflection layer, and is preferably 1 to 30 nm, more preferably 5 to 15 nm.
Further, as a method for imparting an antifouling function to the hard coat layer, a small amount of a hard coating agent in the hard coat layer, for example, a fluorine-based ultraviolet curing antifouling additive in an ultraviolet curing acrylic resin hard coating agent. By adding, in addition to the water repellency and oil repellency characteristic of fluorine as a surface functional material, an excellent antifouling property (prevention of fingerprint adhesion) can be imparted to the surface of the hard coat layer.

(Anti-glare layer)
The display optical filter of the present invention has an anti-glare layer in addition to the functional layer or the optical functional layer, so that reflection of fluorescent light or the like on the display screen can be mitigated by irregularly reflecting external light.
In order to form fine irregularities on the surface of the hard coat layer, molding is performed using a mat-shaped shaping film having fine irregularities on the surface, or a mat material such as resin particles is added to the hard coat agent. Can be done.
Alternatively, the antiglare layer can also be formed by adding irregularities to the surface of the hard coat layer by containing an organic or inorganic filler (fine particles) in the hard coat layer.

The moldable film is fine by applying a resin containing fine particles on a resin film such as a releasable PET film, or on a resin film such as a PET film. What provided the uneven | corrugated layer and formed the shaping layer can be used.
For the mat material, for example, resin particles having high transparency are preferably used. When the refractive index of the mat material is made as close as possible to the refractive index of the resin of the hard coat agent, the transparency of the coating film is not impaired and the antiglare property can be increased.
Examples of such resin particles include acrylic resin particles, polycarbonate resin particles, and polystyrene resin particles. The particle diameter of these resin particles is preferably 1 to 12 μm.

(Antistatic layer)
An antistatic layer is formed on or inside the functional layer or the optical functional layer to prevent dust from adhering to the surface of the optical filter due to static electricity.
In order to completely prevent dust from adhering to the surface of the functional layer or the optical functional layer, the surface resistivity is 1 × 10 ¹⁰ (Ω / □) or less, more preferably 1 × 10 ⁸ (Ω / □) Must be:
In general, the antireflection layer, which is the outermost layer of the functional layer or the optical functional layer, can contain an antistatic agent to serve as the antistatic layer. Moreover, an antistatic agent can be apply | coated on a hard-coat layer and an antistatic layer can be formed. Alternatively, an antistatic agent may be added to the hard coat layer to provide an antistatic function and also serve as an antistatic layer.

Examples of the antistatic agent include fine metal oxide particles such as aluminum oxide, silicon dioxide, titanium dioxide, and zirconium oxide, fine particles of a conductive polymer, and a surfactant.
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
A thin film of an antistatic layer can be formed by a method of directly applying a liquid containing these surfactants onto a resin film.
This antistatic layer can also be formed on the hard coat layer containing the conductive metal oxide fine particles.
As a method for applying the antistatic agent, a known method such as a gravure coater, a micro gravure coater, a die coater, a dip coater, or screen printing can be appropriately selected and used.

(Electromagnetic shielding material for display)
In the present invention, the display electromagnetic shielding material in which only the metal mesh pattern is formed on one surface of the transparent base material is provided on one surface of the long transparent base material supplied by rewinding from the roll body. An electromagnetic wave shielding material provided with a seamless metal mesh pattern in the longitudinal direction of the transparent base material can be cut with the outer dimensions of the display to produce a single-wafer electromagnetic wave shielding material for each display.

  In the present invention, the display electromagnetic shielding material in which the metal mesh pattern is formed on one surface of the transparent base material and the electrode frame is formed around the metal mesh pattern is rewound from the roll body and supplied. An electromagnetic shielding material in which a metal mesh pattern having a screen size of a display is formed on one surface of a long transparent base material, and an electrode frame made of a metal mesh or a metal thin film is disposed around the metal mesh pattern Can be cut by the outer dimensions of the display to produce a single-wafer electromagnetic shielding material for each display.

In addition, on the other surface of the transparent base material on which the metal mesh pattern of the electromagnetic wave shielding material is not formed, a pressure sensitive adhesive layer and a release film subjected to a release treatment on the surface are laminated and placed, for example, a display front glass Bonding to a board can be performed conveniently.
In addition, a protective film with a pressure-sensitive adhesive that has been subjected to a release treatment is placed on the surface of the metal mesh pattern, and the electromagnetic shielding material is attached to the display front glass plate, and then finally peeled off. It is possible to prevent damage to the surface of the metal mesh that is formed and contamination of foreign matter into the concave and convex portions.

  The dimensions and arrangement pattern of the electrode frame in the electromagnetic shielding material for display need to be changed according to the screen size of the display. Typical screen sizes of the display include 42 inches, 50 inches, 60 inches, and 65 inches.

In the electromagnetic wave shielding material for display, it is necessary to adjust the bias angle θ of the metal mesh pattern with respect to the electrode frame in order to minimize the moire generated by the interference between the black matrix pattern of the display and the metal mesh pattern of the electromagnetic wave shielding material. (See FIGS. 3 and 4).
This is because the optimum value of the bias angle θ of the metal mesh pattern with respect to the display screen is determined according to the display resolution.

The following are typical examples of display resolution.
-VGA: 640 x 480 = 310,000 pixels-XGA: 1024 x 768 = 790,000 pixels-SXGA: 1280 x 1024 = 13.1 million pixels-HD: 1280 x 1080 = 1.38 million pixels-Full HD: 1920 x 1080 = 2.07 million Pixel

  The metal mesh pattern needs to be formed so as to have an optimum bias angle θ according to the resolution of the display panel.

  According to the present invention, it is possible to provide an electromagnetic wave shielding material for a display which is excellent in visibility and can be manufactured at a low cost as a whole, and an optical filter for a display using the electromagnetic wave shielding material for a display.

It is a schematic sectional drawing which shows an example of the electromagnetic wave shielding material of this invention. It is a partial detail sectional view of the metal mesh pattern in the electromagnetic wave shielding material of the present invention. It is a schematic plan view which shows an example of the electromagnetic wave shielding material of this invention. It is a schematic plan view which shows the other example of the electromagnetic wave shielding material of this invention. It is a schematic sectional drawing which shows the other example of the electromagnetic wave shielding material of this invention. It is a schematic sectional drawing which shows an example of the electromagnetic wave shielding material by a prior art. It is a schematic sectional drawing which shows an example of the optical filter for displays of this invention. It is a schematic sectional drawing which shows the other example of the optical filter for displays of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent base material, 2 ... Silver halide thin film mesh pattern, 3 ... Fine silver mesh pattern of developed silver, 4 ... Plating layer, 5 ... Blackening treatment layer, 6 ... Metal mesh pattern, 7, 9 ... Electromagnetic shielding material , 8 ... Electrode frame, 10, 12 ... Adhesive layer, 11 ... Front glass plate, 13 ... Near infrared absorbing layer (NIR resin layer), 14 ... Ultraviolet absorbing layer (UVA adhesive layer), 15 ... Transparent substrate (PET) Resin), 16 ... functional layer (AR layer), 17 ... functional film, 18 ... optical functional film, 21 ... resin substrate, 22, 23 ... adhesive layer, 24 ... antireflection layer, 25 ... etching of copper foil Mesh pattern, 26 ... electromagnetic wave shielding material of the prior art, 27 ... a portion where copper foil is dissolved by etching.

Claims (9)

  On one side of the transparent base material, a peeled sheet-like base material is laminated via an adhesive layer, and on the other side of the transparent base material, a fine silver mesh pattern of developed silver generated by a photographic method and A metal mesh pattern made of a plating layer laminated thereon is formed, the metal mesh pattern is a metal mesh pattern according to a screen size of a display, and the surface of the plating layer is blackened, and the metal mesh pattern An electromagnetic wave shielding material for a display, wherein a resin for transparentizing treatment is not embedded in the concave portion of the metal mesh pattern and the metal mesh pattern is exposed to the outside air.   On at least one surface of the transparent substrate, a fine mesh pattern of developed silver produced by a photographic method and a metal mesh pattern composed of a plating layer laminated thereon are formed, and the metal mesh pattern has a screen size of a display. The surface of the plated layer is blackened, and the metal mesh pattern is not exposed to the recesses of the metal mesh pattern, and the metal mesh pattern is exposed to the outside air. An electromagnetic wave shielding material for display.   3. The electromagnetic wave for display according to claim 1, wherein a silver halide thin film mesh pattern is formed on a surface of the developed silver fine line mesh pattern generated by the photographic method in contact with the transparent substrate. Shield material.   The display electromagnetic wave shielding material according to any one of claims 1 to 3, wherein an electrode frame is disposed around the metal mesh pattern.   The fine silver mesh pattern of developed silver produced by the photographic process is one produced by a negative developing method in which developed silver appears in the exposed part, or positive development in which developed silver appears in the unexposed part. 5. The electromagnetic wave shielding material for display according to claim 1, wherein the electromagnetic wave shielding material is for display.   6. The electromagnetic wave shielding material for display according to claim 1, wherein the metal mesh pattern is the outermost surface on the display side of the front glass plate disposed with a gap layer in front of the front panel of the display. An optical filter for display, which is arranged as described above. Between the front glass plate and the electromagnetic wave shielding material for display, at least an ultraviolet absorption layer and a near infrared absorption layer are laminated,
Furthermore, one or more functional layers selected from the group consisting of a hard coat layer, an antistatic layer, an antireflection layer, and an antifouling layer are formed on one side of the transparent substrate on the viewing side of the front glass plate. The functional film formed by laminating a pressure-sensitive adhesive layer on the other surface of the transparent base material is bonded via the pressure-sensitive adhesive layer. Optical filter.   The electromagnetic wave shielding material for display according to any one of claims 1 to 5 is bonded to the display side of a front glass plate disposed with a gap layer in front of the front panel of the display via an adhesive layer. An optical filter for display.   Further, on the surface of the front glass plate on which the electromagnetic wave shielding material for display is not bonded, a near infrared absorbing layer, an ultraviolet absorbing layer, a hard coat layer, an antistatic layer, an antireflection layer, an antifouling layer The optical filter for display according to claim 8, wherein an optical functional film having one or more optical functional layers selected from the group consisting of is bonded via an adhesive layer.

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