JP2008300721A - Electromagnetic wave shielding material roll body for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electromagnetic wave shielding material roll body for display which has high transparency, is excellent in electromagnetic wave shielding performance, suppressed in partial variation of the electromagnetic wave shielding performance, has high productivity, and is supplied in a roll state. <P>SOLUTION: In the electromagnetic wave shielding material roll body for the display, a metal mesh pattern is formed at a fixed interval in the longitudinal direction of a transparent base material, and the roll body is supplied in a roll state. The metal mesh pattern has a conductive mesh pattern and an at least electrolytically plated plating layer on it, a shield frame composed of a metal mesh or a metal thin film is arranged around the metal mesh pattern, and an electric supply layer for electrolytic plating which is in contact with both outer sides in the width direction of the shield frame and whose contact area with an electric supply roller is changed by a position in the longitudinal direction is continuously formed in the longitudinal direction of the transparent base material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electromagnetic wave shielding material roll for display.

  In recent years, there have been increasing opportunities to use electronic devices such as display devices used in mobile phones, personal computers, TVs, etc., but electromagnetic waves are generally emitted from these electronic devices, so that It is known that so-called Electro-Magnetic Interference (EMI) occurs, such as malfunction of electrical equipment, failure, or the possibility of harming the human body. Along with this, there is an increasing need to reduce such EMI, and standards or regulations regarding the intensity of electromagnetic wave emission are established mainly in Europe and the United States, and recent electronic devices are required to meet these standards. Yes. In particular, equipment that requires visibility such as a CRT, a flat panel display, or a window glass needs to satisfy both electromagnetic wave shielding performance and transparency.

  These are generally provided with a conductive metal pattern on a transparent resin film. In order to improve the production efficiency, a continuous metal mesh pattern is formed on the transparent resin film of a long roll, and is necessary. It cut | judged to a suitable size and it uses for an electromagnetic wave shield panel (for example, refer patent documents 1-4).

Examples of a method for producing an electromagnetic shielding material using a conductive metal mesh include the methods shown in the following (1) to (3).
(1) An etching method in which a metal foil is bonded to a transparent substrate or a metal thin film is deposited on the transparent substrate, and then a conductive metal pattern is formed by a photolithographic method.
(2) A printing-plating method in which a conductive metal pattern is printed on a transparent substrate and then plated to form a conductive metal pattern.
(3) A photographic silver-plating method for forming a conductive metal pattern by forming a fine line pattern with metallic silver developed by a photographic method and then physically developing and / or plating the metallic silver (for example, Patent Document 2) And Patent Document 3).

  In the etching method (1), it is a problem from the viewpoint of saving resources that only a very small portion which becomes a thin line portion is left by etching and most other metals are dissolved and removed. In addition, since the maximum standard dimension width of a commercially available metal foil is about 600 mm or less, an electromagnetic wave shielding material having a wider dimension width cannot be produced by the method of bonding the metal foil. In addition, when a metal thin film is deposited, there is a problem that it cannot be easily manufactured because a huge equipment cost is required.

  In the printing-plating method (2), it is difficult to reduce the line width of the mesh pattern to 30 μm or less, and there is a problem that the adhesiveness between the transparent substrate and the mesh pattern is poor and is easily peeled off.

  In the photographic silver-plating method of (3) above, high electromagnetic shielding properties can be obtained, and there is no restriction on the dimensions of the transparent substrate, so that it can be produced by roll-to-roll and has very high productivity. This is a preferred production method.

  By the way, in the photographic silver-plating method, when the fine mesh pattern is formed by electroless plating and / or electrolytic plating on the developed metallic silver of the mesh pattern, the electroless plating has a slow plating speed. There were problems such as difficulty in quality control of the electrolytic plating solution and high manufacturing cost.

  Also, in the case of electrolytic plating, the plating speed is faster than that of electroless plating, but in the prior art, electrolytic plating is intermittently performed for each mesh pattern by transferring to the electrolytic cell by step feed for electrolytic plating. There is a problem that productivity is low because it is performed by feeding.

  In addition, when performing electroplating in a continuous process, it is technically difficult to uniformly and stably supply power to supply electrolysis current, resulting in uneven plating thickness in part of the mesh pattern. As a result, there is a problem that a part of the mesh pattern has a partial variation in electromagnetic shielding performance.

  As these countermeasures, in Patent Document 5, a metal mesh pattern is provided in the longitudinal direction of the transparent base material at a predetermined interval, and the metal mesh pattern is a developed silver mesh pattern generated by a photographic method and a top thereof. At least a plating layer that is electroplated, a shield frame made of a metal mesh or a metal thin film is disposed around the metal mesh pattern, and a power supply layer for electrolytic plating having a constant width in contact with both outer sides in the width direction of the shield frame Is an electromagnetic wave shielding material roll body for display provided continuously in the longitudinal direction of the transparent substrate, that is, an electromagnetic wave shielding material roll body for display is obtained by feeding power to the continuous power feeding layer by continuous feed, continuous plating, and power feeding roll. A method is disclosed.

This method enables continuous plating with a feed roller by forming a continuous feed layer, which improves productivity. However, using a continuous electrolytic plating conductive layer with a constant width, it turns out that “plating unevenness” increases. It was. This is because the electrolytic current necessary for uniform electrolytic plating differs depending on the position in the longitudinal direction of the electromagnetic wave shielding material roll for display, so the power supply amount is always the same when the width of the electrolytic plating power supply layer is the same, and the plating thickness This is to cause variation.
International Publication No. 01/051276 Pamphlet JP 2004-221564 A International Publication No. 04/007810 Pamphlet International Publication No. 06/088059 Pamphlet JP 2007-67269 A

  The present invention has been made in view of the above problems, and its purpose is to have high transparency, excellent electromagnetic shielding performance, little variation in electromagnetic shielding performance, high productivity, and supply in a roll state. It is in providing the electromagnetic wave shielding material roll body for displays.

  The above object of the present invention is achieved by the following configurations.

  1. An electromagnetic wave shielding material for a display in which a metal mesh pattern having a screen size of a display is provided on at least one surface of a long transparent base material at regular intervals in the longitudinal direction of the transparent base material and is supplied in a roll state The metal mesh pattern has a conductive mesh pattern and at least a plating layer electroplated thereon, and a shield frame made of a metal mesh or a metal thin film is disposed around the metal mesh pattern. In addition, a power supply layer for electrolytic plating that is in contact with both outer sides in the width direction of the shield frame and whose contact area with the power supply roller changes depending on the position in the longitudinal direction is provided continuously in the longitudinal direction of the transparent substrate. An electromagnetic shielding material roll body for display, characterized by:

  2. 2. The electromagnetic wave shielding material roll for display according to 1, wherein the power feeding layer is made of a metal thin film or a metal mesh.

  3. 3. The electromagnetic wave shielding material roll for display according to 1 or 2, wherein a contact area of the power feeding layer with the power feeding roller is changed by changing a width of the power feeding layer.

  4). 3. The display electromagnetic wave shielding material roll according to claim 1 or 2, wherein a contact area of the power feeding layer with the power feeding roller is changed by changing a mesh pattern of the power feeding layer.

  5. 5. The electromagnetic wave shielding material roll for display according to any one of 1 to 4, wherein the shield frames on both sides in the longitudinal direction are continuous.

  6). The electromagnetic wave shielding material roll for display according to any one of 1 to 5, wherein a contact area between the power feeding layer and the power feeding roller is smaller than a central portion of the shield frame around a boundary of the shield frame. body.

  7. The electromagnetic wave shield for display according to any one of 1 to 6, wherein at least a part of the conductive mesh pattern, the shield frame, and the power feeding layer is developed silver produced by a photographic method. Material roll body.

  According to the present invention, there is provided an electromagnetic wave shielding material roll for display that is supplied in a roll state, having high transparency, excellent electromagnetic wave shielding performance, little partial variation in electromagnetic wave shielding performance, and high productivity. Can do.

  As a result of intensive studies in view of the above problems, the present inventors have found that a metal mesh pattern having a screen size of the display is arranged at a constant interval in the longitudinal direction of the transparent substrate on at least one surface of the long transparent substrate. An electromagnetic wave shielding material roll for display, which is provided and supplied in the form of a roll, wherein the metal mesh pattern has a conductive mesh pattern and a plating layer at least electroplated thereon, the metal mesh pattern A shield frame made of a metal mesh or a metal thin film is disposed around the outer periphery of the shield frame, in contact with both outer sides in the width direction of the shield frame, a power supply layer for electrolytic plating whose contact area with the power supply roller changes depending on the position in the longitudinal direction, The display electromagnetic wave shielding material roll provided continuously in the longitudinal direction of the transparent base material has high transparency. , Found that an electromagnetic shielding material roll body for display supplied in a roll state can be obtained, which is excellent in electromagnetic shielding performance, has little variation in electromagnetic shielding performance, and has high productivity. is there.

  Hereinafter, the present invention will be described in detail.

(Feeding layer)
The present invention is characterized in that a power supply layer for electrolytic plating whose contact area with the power supply roller changes depending on the position in the longitudinal direction of the transparent substrate is provided continuously in the longitudinal direction of the transparent substrate. The electromagnetic shielding material roll for display has different electrolytic currents required for electrolytic plating depending on the position in the longitudinal direction. Specifically, the required electrolysis current is smaller around the boundary of the shield frame than in the central portion of the shield frame. In the present invention, the amount of electrolysis current supplied can be adjusted by changing the contact area between the power supply layer and the power supply roller, and the plating unevenness is greatly reduced. Moreover, since the power feeding layer is continuously provided in the longitudinal direction of the transparent substrate, continuous plating is possible, and high productivity is obtained.

  Examples of means for changing the contact area between the power supply layer and the power supply roller include a method of changing the width of the power supply layer and a method of changing the size of the mesh by forming the power supply layer with a mesh.

  The power feeding layer, the conductive mesh pattern, and the shield frame can be produced with a conductive paste by a printing method, but developed silver produced by a photographic method is preferable. As described above, the photographic manufacturing method provides high electromagnetic shielding properties, is not restricted by the dimensions of the transparent base material, and can be manufactured roll-to-roll and has very high productivity.

  The present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic view showing an example of an electrolytic plating apparatus suitably used for plating the electromagnetic wave shielding material roll for display according to the present invention. FIG. 2 is a partial plan view showing an example of the arrangement of the mesh pattern and the power feeding layer in the electromagnetic wave shielding material roll for display according to the present invention. FIG. 3 is a partial plan view showing an example of the arrangement of mesh patterns and power feeding layers in a conventional electromagnetic wave shielding material for a display.

  In the electroplating apparatus 1 shown in FIG. 1, a roll sheet 3 having a mesh pattern, a shield frame, and a power feeding layer is formed on at least one surface of a long transparent substrate from a raw roll 2 wound in a roll shape. Then, it is transferred from the left to the right in FIG. First, the roll sheet 3 is passed through the water washing tank 5 and washed to remove unnecessary foreign matters and contaminants. If necessary, it is passed through an electroless plating tank (not shown) and electrolessly plated on the developed silver mesh pattern, and then transferred to at least the electrolytic plating tank 6.

  In the electrolytic plating tank 6, electrolytic plating is performed between the power supply roll 7 serving as the cathode and the positive electrode plate 8 serving as the anode through the electrolytic plating solution 9, thereby forming the conductive mesh pattern of the roll sheet 3 and / or on the conductive mesh pattern. An electrolytic plating layer is deposited on the electroless plating layer. The temperature of the electrolytic plating solution 9 is controlled by a temperature regulator (not shown) so as to be a predetermined temperature. The power supply roll 7 is provided at an entrance for the roll sheet 3 to enter and exit the electrolytic plating tank 6, and the electrolytic plating solution 9 can leak from the gap of the power supply roll 7 and the like of the electrolytic plating tank 6 and fall. For this reason, a receiving tank 10 for receiving the leaked electrolytic plating solution 9 is installed below the electrolytic plating tank 6, and the electrolytic plating solution 9 received in the receiving tank 10 passes through the circulation pump 11 and the filter 12 again. It is configured to recirculate to the electrolytic plating tank 6.

  The roll sheet 3 exiting the electrolytic plating tank 6 is washed away with an unnecessary electrolytic plating solution 9 in a water washing tank 13, drained and dried in a dryer 14, wound up again, and rolled up to form a roll-shaped electromagnetic shielding material roll 15. It becomes.

  Here, in the present invention, when electrolytic plating is performed in the electrolytic plating tank 6, a feeding layer for electrolytic plating provided continuously in the longitudinal direction on the roll sheet 3 (the feeding layer and the feeding roller depending on the position in the longitudinal direction). Power is supplied to the mesh pattern 22 through the power supply layers 25A and 25B (FIG. 2) whose contact area changes with the power supply.

  In the prior art, like a roll sheet 30 shown in FIG. 3, a mesh pattern 32 of a display screen size and a shield frame 33 around the mesh pattern 32 are arranged on a long transparent substrate 31 at a constant interval 34. A structure in which a power feeding layer 35 is provided on both outer sides in the width direction of each shield frame 33 is used. In the prior art, the roll sheet 30 is transferred stepwise by the transfer roll 4, the roll sheet 30 is intermittently introduced into the electrolytic plating tank 10, and a mesh pattern corresponding to one screen size in the electrolytic plating tank 10. This is an intermittent method in which electrolytic plating is performed every 32. For this reason, in the prior art, the supply and transfer of the roll sheet 30 are stopped for a certain period of time in each plating step in which each mesh pattern 32 is electroplated, and thus productivity is limited to a low level. It was.

  Therefore, in the present invention, the exposed and developed roll sheet 3 is continuously fed out from the raw roll 2 and transferred to the electrolytic plating tank 6 by the continuous feed of the transfer roll 4 to perform electrolytic plating. Like the roll sheet 20, a mesh pattern 22 having a screen size of the display at a constant interval 24 on at least one surface of the long transparent base material 21 and a shield frame made of a metal mesh or a metal thin film around the mesh pattern 22 The power supply layers 25 </ b> A and 25 </ b> B are provided which are in contact with both outer sides in the width direction of the shield frame 23 and change in contact area with the power supply roller 7 depending on the position in the longitudinal direction. The power supply layers 25A1 and 25B1 near the boundary between the shield frames of the power supply layers 25A and 25B are narrow and mesh, respectively, and the electrolytic current flowing through the mesh pattern 22 through this portion is reduced.

  The continuous power supply layers 25 </ b> A and 25 </ b> B are in contact with the power supply roll 7 serving as a cathode before and after the place where the roll sheet 20 is introduced into the electrolytic plating tank 6. Thus, during electrolytic plating, an electrolytic current is supplied to the mesh pattern 22 through the power supply layers 25A and 25B, and a plated layer by electrolytic plating is formed on the metal mesh pattern.

  The mesh pattern 22 which is the screen size of the display is a metal mesh pattern in the raw roll 2. That is, the raw fabric roll 2 has a mesh pattern 22, a shield frame 23 made of a metal mesh or a metal thin film, and a power supply layer 25 </ b> A in the longitudinal direction of the transparent substrate 21 on at least one surface of the long transparent substrate 21. , 25B. Moreover, the mesh pattern 22 in the electromagnetic wave shielding material roll body is obtained by forming a plating layer on the raw metal mesh pattern at least by electrolytic plating. The power supply layers 25A and 25B are made of a metal mesh or a metal thin film, and preferably have a width of 15 to 80 mm.

(Transparent substrate)
In the present invention, a normal synthetic resin film can be used as a long transparent substrate (hereinafter also simply referred to as a support).

  For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, polyether ketone film, Polyetherketoneimide film, polyamid Film, fluororesin film, a nylon film, a polymethyl methacrylate film or an acrylic film or the like. In addition to these plastic films, quartz glass, soda glass, and the like can be used.

  Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone), polyethylene terephthalate film, and polyethylene naphthalate film are preferably used. In the present invention, it is particularly preferable to use a polyethylene terephthalate film or a polyethylene naphthalate film that is a polyester film as the support from the viewpoints of transparency, isotropic properties, adhesiveness, durability, and the like.

  When the electromagnetic wave shielding material roll for display according to the present invention is used for a display screen of a display, high transparency is required, and therefore it is desirable that the support itself has high transparency. The average transmittance in the visible light region of the plastic film or glass plate as the support in this case is preferably 85 to 100%, more preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film or glass plate to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator. The average transmittance in the visible light region is obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region of 400 to 700 nm at least every 5 nm, and obtaining the average value thereof. Define. In measurement, the measurement aperture needs to be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least an area 100 times larger than the mesh area of the mesh.

  The support used in the present invention is 100 m or more, more preferably 500 m or more, still more preferably 1000 m or more and 2000 m or less in order to produce the continuous support as a long roll.

  The width of the support used in the present invention is 1 m or more, preferably 1.5 m or more, and more preferably 2 m or more and 5 m or less because of the demand for a display panel with a larger screen.

  Although there is no restriction | limiting in particular in the thickness of the support body used for this invention, It is preferable that it is 5-200 micrometers from a viewpoint of the maintenance of a transmittance | permeability, and a handleability, and it is further more preferable that it is 30-150 micrometers.

(Mesh part)
The line width of the conductive metal mesh portion formed to shield electromagnetic waves is usually 20 μm or less, preferably 18 μm or less, more preferably 15 μm or less, more preferably 3 μm or more, from the viewpoint of making the mesh inconspicuous. 10 μm or less is most preferable. If it is less than 3 μm, the conductivity is slightly insufficient.

  The line spacing of the mesh part is preferably 150 μm or more, more preferably 180 μm or more, and particularly preferably 200 μm or more. The thickness of the fine mesh wire is preferably 0.1 μm or more and 25 μm or less, more preferably 0.2 or more and 20 μm or less, and particularly preferably 0.5 μm or more and 15 μm or less.

  In the mesh portion of the present invention, the aperture ratio is preferably larger than 80%, more preferably 85% or more, and most preferably 90% or more from the viewpoint of visible light transmittance. The aperture ratio is the ratio of the portion without fine lines forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%.

  In the present invention, in order to give high translucency and high electromagnetic wave shielding performance, a lattice-like fine line mesh pattern is drawn by exposure, and then a development process or the like is performed to form a conductive mesh pattern. It is preferable to use an electromagnetic shielding material roll for display.

(Shield frame)
It is known that the shielding ability of the electromagnetic shielding material is improved by grounding the conductive portion. In an electromagnetic shielding material for display, in order to make it easy to ground the mesh portion, a solid portion electrically connected to the mesh portion called a so-called frame edge is generally provided around the mesh portion. The solid portion has a width of 2 cm to 15 cm and is provided for the purpose of expanding the contact area when electrically contacting a metal plate connected to the ground (ground potential).

  In the present invention, a shield frame made of a metal mesh or a metal thin film is used. In the case of a metal mesh, a geometric pattern is preferable. A geometric pattern is a pattern in which basic figures such as polygons, circles, ellipses, and stars are continuously arranged. In order to make the conductivity of the shield frame higher than that of the mesh part, the aperture ratio should be made smaller than the mesh part, the pitch should be made smaller than the mesh part, the line width should be made larger than the mesh part, In some cases, the thickness of the fine line is increased.

  In the present invention, it is preferable that the shield frames on both sides in the longitudinal direction are continuous, because the width of the electrolytic current required for the electrolytic plating that varies depending on the position in the longitudinal direction is small.

  The electromagnetic shielding material roll for display has different electrolytic currents required for electrolytic plating depending on the position in the longitudinal direction. Specifically, the required electrolysis current is smaller around the boundary of the shield frame than in the central portion of the shield frame. In the present invention, the amount of electrolysis current supplied can be adjusted by changing the contact area between the power supply layer and the power supply roller, and the plating unevenness is greatly reduced. Moreover, since the power feeding layer is continuously provided in the longitudinal direction of the transparent substrate, continuous plating is possible, and high productivity is obtained.

  In addition, when the shield frames on both sides in the longitudinal direction are continuously formed, it is necessary to cut two adjacent shield frames in the middle (arrow portion in FIG. 2) for commercialization. It is also possible to form the mark by using the shape of the power feeding layer.

(Mesh formation method)
In the electromagnetic wave shielding material roll for display according to the present invention, a method for forming a conductive mesh having an electromagnetic wave shielding function is a known method, that is, vapor deposition, various printing methods (gravure printing, screen printing, ink jet printing, etc.), etching. The silver salt photographic method can be used in which a silver halide photosensitive material is formed by exposure, development processing, and intensification processing as necessary.

  When forming the electromagnetic wave shielding material roll for display of the present invention using a silver salt photographic method, a silver halide emulsion layer containing a photosensitive silver halide and a binder described later is provided on the support. In addition to this, the silver halide emulsion layer may contain a hardening agent, a contrast enhancer, an activator and the like.

(Photosensitive silver halide)
In the present invention, the content of photosensitive silver halide in terms of silver in 0.05 g / m ² or more, preferably less than 3 g / m ^2, particularly preferably in terms of silver 0.3 g / m ² or more, It is less than 1 g / m ² . When the photosensitive silver halide content is less than 0.05 g / m ² , it is difficult to obtain sufficient electromagnetic wave shielding performance. This is presumably because the amount of developed silver nuclei serving as a catalyst for physical development or metal plating treatment described later becomes insufficient, and it becomes difficult to form an effective conductive mesh. In addition, when the photosensitive silver halide content is 3 g / m ² or more, the amount of silver halide relative to the binder is relatively large, so that the coating tends to become brittle and maintain sufficient coating strength. It becomes difficult.

  When the amount of the binder is increased to maintain the physical properties of the film, the distance between the grains of the photosensitive silver halide increases, so that it becomes difficult to form a developed silver network, it is difficult to form an effective conductive mesh, and the temperature Further, the durability against humidity change becomes insufficient, and the effect of the present invention is hardly obtained.

In the present invention, the binder amount of the silver halide light-sensitive material is particularly preferably 10 mg / m ² or more and 0.2 g / m ² or less from the viewpoint of achieving both conductivity and film properties. When the amount of the binder is less than 10 mg / m ^2, the amount of silver halide relative to the binder is relatively large, so that the coating tends to become brittle and it is difficult to maintain sufficient coating strength. In addition, when the amount of the binder is more than 0.1 g / m ² , the distance between the photosensitive silver halide grains is increased, so that it is difficult to form a developed silver network, and it is difficult to form an effective conductive mesh. In addition, the durability against changes in temperature and humidity becomes insufficient, and the effects of the present invention cannot be obtained.

  The composition of the silver halide grains used in the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, in order to obtain metallic silver having good conductivity, fine grains having high sensitivity are preferable, and silver iodobromide grains are preferably used. When a large amount of iodine is contained, the sensitivity is high and the particles can be made fine.

  In order to reduce the surface specific resistance after silver halide grains are developed to become metallic silver grains and effectively shield electromagnetic waves, the contact area between developed silver grains needs to be as large as possible. For this purpose, a smaller silver halide grain size is better to increase the surface area ratio, but too small grains tend to agglomerate into large agglomerates, in which case the contact area will be reduced, so there is an optimum grain size. To do. In the present invention, the average grain size of the silver halide grains is preferably 0.01 to 0.5 μm, more preferably 0.03 to 0.3 μm, in terms of a sphere equivalent diameter. In addition, the sphere equivalent diameter of silver halide grains represents the diameter of grains having the same volume and having a spherical shape. The average grain size of silver halide grains is the temperature at the time of preparation of silver halide grains, pAg, pH, addition rate of silver ion solution and halogen solution, grain size control agent (for example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be appropriately combined and controlled.

In the present invention, the value obtained by dividing the coating silver amount (g / m ² ) by the particle size (μm) is preferably 6 to 25. When a large amount of photosensitive silver halide having a relatively small particle size is used, this value tends to be larger than 25. In this case, the silver halide grains slip off from the coating at the edge when the film is cut. It tends to be easier. Further, when a small amount of photosensitive silver halide having a relatively large particle diameter is used, this value tends to be smaller than 6, and in this case, the number of photosensitive silver halide grains in a unit area is reduced, so that This is because it tends to decrease.

  In the present invention, the shape of the silver halide grains is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, tetragonal flat plate, etc.), octahedron, tetrahedron It can be in various shapes such as shapes. In order to increase the sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used. The particle size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of enhancing the transparency while sharply reproducing the outline of the pattern and maintaining high conductivity during pattern formation by exposure. The particle size distribution of the silver halide grains used in the silver halide photosensitive material according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(In the formula, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The silver halide grains used in the present invention may further contain other elements. For example, in a photographic emulsion, it is also useful to dope metal ions used to obtain a high-contrast emulsion. In particular, Group 8-10 metal ions such as iron ion, rhodium ion, ruthenium ion and iridium ion are preferably used because the difference between the exposed portion and the unexposed portion tends to be clearly generated when the metal silver image is generated.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such a ligand include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and the like. Specific examples of the compound include potassium bromide rhodate and potassium iridate.

In the present invention, the content of the metal ion compound contained in the silver halide is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, and is preferably 10 ⁻⁹ to 10 ^−. More preferably, it is ³ mol / mol Ag.

  In order for silver halide grains to contain the above-described metal ions, the metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add in the arbitrary places in a process. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

  In the present invention, in order to further improve the sensitivity, chemical sensitization performed with a photographic emulsion or spectral sensitization can be performed.

(binder)
In the silver halide light-sensitive layer according to the present invention (a layer comprising at least light-sensitive silver halide and a binder), silver halide grains are uniformly dispersed, and the silver halide grains are supported on a support, and halogenated. A binder is used for the purpose of ensuring the adhesiveness between the silver photosensitive layer and other layers or the support. The binder that can be used in the present invention is not particularly limited, and any of a water-insoluble polymer and a water-soluble polymer can be used. From the viewpoint of improving developability, it is preferable to use a water-soluble polymer.

  In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose Hydrophilic colloids such as synthetic hydrophilic polymer materials such as derivatives, mono- or copolymers can also be used.

  In the present invention, the silver / binder mass ratio of the silver halide photosensitive layer is preferably from 0.5 to 20. This is to increase the contact area between the developed silver particles described above, more preferably 1.0 to 10, and even more preferably 3.0 to 8.0.

(Layer structure of silver halide photosensitive material)
The layer structure of the silver halide photosensitive material used for forming the electromagnetic wave shielding material roll for display of the present invention basically comprises a support and a silver halide photosensitive layer. Furthermore, it is preferable to provide various layers in consideration of not only high functionality, processing characteristics and durability as an electromagnetic shielding material roll for display but also production efficiency and production stability of the silver halide photosensitive material.

  For example, a non-photosensitive intermediate layer is provided between the support and the silver halide photosensitive layer, a backing layer is provided on the opposite side of the transparent substrate from the silver halide photosensitive layer, or the silver halide is provided. It is preferable to provide a protective layer on the photosensitive layer. These layers may be composed of a plurality of layers.

  In the present invention, it is also preferred that a silver halide photosensitive layer is provided on each side of the support and a conductive pattern is formed on each. In this case, it is preferable that the silver halide emulsion coated on each surface has sensitivity at different wavelengths by spectral sensitization or the like. By giving sensitivity to different wavelengths on the front and back surfaces, it becomes possible to create different conductive patterns on each surface, for example, to selectively shield against electromagnetic waves of different frequencies on the front and back surfaces. It is also possible to form a conductive pattern.

(Method for producing electromagnetic shielding material roll for display)
The method for producing an electromagnetic wave shielding material roll for display according to the present invention comprises a silver halide photosensitive material in which a layer comprising at least a photosensitive silver halide and a binder is coated on a long transparent substrate, and after pattern exposure, development. Processing and plating are performed to form a continuous conductive mesh portion and a shield frame having a geometric pattern.

  Therefore, basically, (1) a step of forming a silver halide photosensitive material by coating a silver halide emulsion on a transparent substrate, (2) a step of pattern exposing the silver halide photosensitive material, (3) It comprises a step of developing the exposed silver halide photosensitive material and (4) a step of plating the developed silver halide photosensitive material, but the pretreatment of the transparent substrate before coating the silver halide emulsion And undercoating process, drying and aging process of the coated silver halide photosensitive material, physical development process before plating of developed silver halide photosensitive material, stabilization process such as pressure heating after plating process You may provide the process to do.

  Each of these steps may be batch-processed independently, but it is preferable that each step is linked to a continuous web from the feeding of the support. Finally, the formed electromagnetic shielding material roll for display may be obtained as a long roll, or may be cut into a necessary size and accumulated in a sheet form.

(Coating process)
A coating process is a process of apply | coating the said structural layer on a support body. Examples of the coating method include dip coating, spray coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, inkjet coating, or US Pat. No. 2,681,294. Examples include an extrusion coating method using the hopper described in the specification. If necessary, U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898 and 3,526,528, Yuji Harasaki, “ The method of simultaneously applying two or more layers described in “Coating Engineering” on page 253 (published by Asakura Shoten in 1973) can also be preferably used.

  In the present invention, in order to make the shield frame more conductive than the mesh portion, a frame mesh portion having a large thickness is formed by thickly applying a region corresponding to the shield frame at the time of silver halide emulsion coating. Can do.

(Exposure process)
In the present invention, the silver halide photosensitive material is exposed in order to form a conductive pattern by performing at least one selected from development processing, physical development and plating processing described later. Examples of the light source used for exposure include light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as electron beams and X-rays. Visible rays are used in terms of utilizing the characteristics of silver halide. Is preferred. In particular, the use of a light source having a narrow wavelength distribution is preferable because formation of an electromagnetic shielding material roll for display can be efficiently controlled and can be stably produced.

  In the present invention, it is particularly preferable to perform exposure using a laser beam. Among various laser beams, a blue laser is preferable because of the photosensitive characteristics of silver halide. The emission wavelength is preferably 370 to 450 nm, particularly 415 to 440 nm.

Specifically, a helium-cadmium laser (about 442 nm), a blue semiconductor laser using an InGaN-based material with an oscillation wavelength of 400 to 430 nm, a GaAlAs-based (laser wavelength 850 nm) semiconductor laser, an MgO: LiNbO ₃ SHG crystal. However, a blue semiconductor laser is preferable from the viewpoints of compactness, low power consumption, stability, long life, and the like. In particular, a blue semiconductor laser announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001 is preferred.

  In the present invention, in order to make the shield frame more conductive than the mesh portion, when exposing the area corresponding to the shield frame of the silver halide photosensitive material, the geometric pattern pitch is exposed to be smaller than that of the mesh portion. The frame mesh portion can be formed by exposing the line width of the geometric pattern to be thick.

(Development processing)
In the present invention, after the silver halide photosensitive material is exposed, development processing is performed. The development process is preferably a so-called black-and-white development process that does not contain a color developing agent.

  As the developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinonesulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1- Use in combination with pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate. Can do. Further, it is preferable to use a reductone compound such as ascorbic acid or isoascorbic acid in combination with the superadditive developing agent without using hydroquinone.

  In addition, sodium sulfite or potassium sulfite as a preservative, sodium carbonate or potassium carbonate as a buffer, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used in the developing solution.

  The development processing solution used in the development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

  In the present invention, it is preferable that the development processing performed after exposure includes physical development before fixing. The term “physical development before fixing” as used herein refers to a process in which silver ions are supplied from outside the silver halide grains having a latent image by exposure to reinforce developed silver before performing a fixing process described later. As a specific method for supplying silver ions from the developing solution, for example, a method of dissolving silver nitrate or the like in advance in a developing solution and dissolving silver ions, or sodium thiosulfate in the developing solution, Examples include a method in which a silver halide solvent such as ammonium thiocyanate is dissolved, unexposed silver halide is dissolved during development, and development of silver halide grains having a latent image is supplemented.

  In the present invention, it is preferable to use a formulation in which a silver halide solvent is preliminarily dissolved in a developer because a reduction in the transmittance of the film due to fogging in unexposed areas can be suppressed.

  In the present invention, in order to make the shield frame more conductive than the mesh portion, the development processing reaction in the area corresponding to the shield frame can be promoted during the development processing of the silver halide photosensitive material. Specifically, this is achieved by increasing the liquid temperature in the vicinity of the shield frame equivalent region or increasing the liquid agitation in the vicinity of the shield frame equivalent region in the developing solution. Needless to say, in the portion where the development processing reaction is promoted, the silver development rate is increased and more developed silver is formed than in the mesh portion, and a frame mesh having a large line width and thickness can be formed.

  In the development processing according to the present invention, after the development of the exposed silver halide grains, fixing processing is performed for the purpose of removing and stabilizing the unexposed silver halide grains. For the fixing treatment in the present invention, a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used. The fixing solution used in the fixing process may use sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like as a fixing agent. Aluminum sulfate, chromium sulfate, or the like can be used as a hardener for fixing. As the fixing agent preservative, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and citric acid, oxalic acid, and the like can be used.

  The washing water used in the present invention includes N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, and N-methyl-isothiazole-4,5 as antifungal agents. -Dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, hydrogen peroxide and the like can be used.

(Reinforcement processing)
In the present invention, in order to assist the contact between the developed silvers formed by the above-described development process and to increase the conductivity, it is preferable to perform a reinforcement process. In the present invention, the intensifying process refers to a process in which a conductive substance source not contained in the silver halide light-sensitive material is supplied from the outside during the development process or after the process to increase the conductivity. Examples of such methods include physical development or plating treatment.

(Physical development processing)
Physical development can be performed by immersing a silver halide photosensitive material having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent.

  In the present invention, physical development is defined not only when the development start point of physical development is the latent image nucleus but also when developed silver is the physical development start point, and this can be preferably used.

(Plating treatment)
In the present invention, various conventionally known plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be performed alone or in combination. Among these, electrolytic plating excellent in selectivity of plating metal, adjustment of plating speed, and plating strength can be preferably used in the present invention. In the case of electroless plating, there is an advantage that uneven plating due to uneven current distribution does not occur. As a metal that can be used for plating, for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used. It is particularly preferable to use copper electrolytic plating from the viewpoint that the plating process is relatively easy and high conductivity is easily obtained.

  The above processing can be performed during development, at any timing after development, before fixing, and after fixing processing. However, from the viewpoint of maintaining high transparency of the film, it is preferably performed after the fixing processing.

  In the present invention, an aspect in which the amount of metal applied by physical development or metal plating is 10 to 100 times in terms of mass with respect to developed silver obtained by exposing and developing a silver halide photosensitive material. preferable. This value can be determined by quantifying the metal contained in the silver halide light-sensitive material by, for example, fluorescent X-ray analysis before and after physical development or metal plating. When the amount of metal applied by physical development or metal plating is less than 10 times in terms of mass with respect to developed silver obtained by exposing and developing a silver halide photosensitive material, conductivity is slightly reduced. If the ratio is larger than 100 times, the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive mesh pattern portion. In the present invention, it is preferable to perform both physical development and metal plating.

  In the present invention, in order to make the shield frame more conductive than the mesh portion, the plating reaction in the area corresponding to the shield frame can be promoted during the plating process. Specifically, in the plating solution, increase the liquid temperature near the area corresponding to the shield frame, increase the liquid agitation near the area equivalent to the shield frame, or increase the current by bringing the electrode closer to the area equivalent to the shield frame. Achieved by etc. Needless to say, in the portion where the plating treatment reaction is promoted, the plating reaction rate is increased and plating is formed more than the mesh portion, and a frame mesh having a large line width and thickness can be formed.

  Furthermore, in the present invention, the region corresponding to the shield frame can be gold-plated in order to make the shield frame more conductive than the mesh portion. Gold plating can be applied to the gold plating solution only after the development process, or after the development silver after development and physical development is formed, and even after copper plating is applied on the development silver. Can be dipped in gold.

  Furthermore, in the present invention, in order to make the shield frame more conductive than the mesh portion, the area corresponding to the shield frame can be pressurized, heated, or heated after pressurization.

  The pressure is 1 kPa to 100 MPa, preferably 10 kPa to 10 MPa, and more preferably 50 kPa to 5 MPa. If the pressure is less than 1 kP, the effect of improving the conductivity is small, and if it is greater than 100 MPa, it is difficult to keep the surface smooth, and haze increases.

  The heating is 40 to 300 ° C, preferably 50 to 200 ° C, more preferably 60 to 200 ° C. If it is less than 40 ° C., the effect of improving conductivity is small, and if it is higher than 300 ° C., it is difficult to keep the surface smooth.

(Oxidation treatment)
In the present invention, it is preferable to carry out an oxidation treatment after the development treatment, physical development or plating treatment. By the oxidation treatment, unnecessary metal components can be ionized and dissolved and removed, and the transmittance of the film can be further increased.

  As the treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, or hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, perhalogenate. A treatment solution containing a conventionally known oxidant such as a method of treating with an aqueous solution containing a peroxide such as a hypohalite, a halogenate, or an organic peroxide can be used. The oxidation treatment is preferably performed after completion of the development treatment and before the plating treatment because the transmittance can be efficiently improved in a short time treatment, and particularly preferably after completion of the physical development.

(Blackening treatment)
In the present invention, it is preferable to perform blackening treatment on the surface of the metal mesh from the viewpoint of preventing reflection of external light on the surface of the electromagnetic wave shielding material roll for display. When the electromagnetic wave shielding material roll body for a transparent display subjected to such blackening treatment is used for a display such as a PDP (plasma display panel), for example, it is possible to reduce a decrease in contrast due to reflection of external light, and when not in use. It is preferable because the color tone of the screen can be kept black and high quality. The blackening treatment method is not particularly limited, and known methods can be used alone or in combination as appropriate. For example, when the outermost surface of the conductive pattern is made of metallic copper, a method of oxidizing by immersing in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate, or copper pyrophosphate, potassium pyrophosphate, A method of blackening by immersion in an aqueous solution containing ammonia and electrolytic plating can be preferably used. If the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy coating, immerse it in an acidic blackening solution containing copper (II) chloride or copper (II) sulfate, nickel chloride or nickel sulfate, and hydrochloric acid. The method to do can be used preferably.

  In addition to the above-described method, the blackening treatment can be performed by a method of finely roughening the surface. However, from the viewpoint of maintaining high conductivity, oxidation is more effective than finer roughening of the surface. A blackening treatment method is preferred.

(Near-infrared absorbing layer)
When the electromagnetic wave shielding material roll for display of the present invention is used in combination with, for example, an optical filter for PDP, a near infrared absorbing layer which is a layer containing a near infrared absorbing dye under a silver halide photosensitive layer It is also preferable to provide In some cases, the near-infrared absorbing layer may be provided on the opposite side of the support to the silver halide emulsion layer side, or may be provided on both the silver halide emulsion layer side and the opposite side. A near infrared absorption layer can be provided between the silver halide emulsion layer containing silver halide and the support, or a near infrared absorption layer can be provided on the opposite side of the support as viewed from the silver halide emulsion layer. The former is preferred because it can be applied simultaneously with one side of the support.

  Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for absorption of heat rays and noise prevention of electronic devices. For this purpose, a dye having a near-infrared absorbing ability having a maximum absorption wavelength of 750 to 1100 nm is preferable, and a metal complex, aminium, phthalocyanine, naphthalocyanine, diimonium, and squalium compound are particularly preferable.

  As a near-infrared absorbing dye, diimonium compounds are IRG-022, IRG-040 (above, manufactured by Nippon Kayaku Co., Ltd.), and nickel dithiol complex compounds are SIR-128, SIR-130, SIR-132, SIR-159. , SIR-152, SIR-162 (manufactured by Mitsui Chemicals, Inc.), and phthalocyanine compounds may be commercially available products such as IR-10, IR-12 (manufactured by Nippon Shokubai Co., Ltd.).

  When the electromagnetic shielding material roll for display of the present invention is used in combination with, for example, an optical filter for PDP, in order to prevent deterioration in color reproducibility due to emission lines of neon gas used in PDP, light near 595 nm is used. It preferably contains an absorbing dye. Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments and organic dyes such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, and metal complex-based materials, and inorganic pigments may be mentioned. Among these, phthalocyanine-based and anthraquinone-based dyes are particularly preferably used because of good weather resistance.

(UV absorbing layer)
In the present invention, it is preferable to use an ultraviolet absorber having a maximum absorption wavelength of less than 350 nm in order to avoid deterioration of the electromagnetic wave shielding material roll for display due to ultraviolet rays.

  As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S-triazine compounds, cyclic imino ester compounds and the like can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is blended with the polyester, a cyclic imino ester compound is particularly preferable. There are no particular restrictions on the layer added to these ultraviolet absorbers, but from the viewpoint of preventing the binder used in the silver halide photosensitive layer (mesh pattern layer) from being deteriorated by ultraviolet rays, it is added to the silver halide photosensitive layer. Alternatively, it is preferably provided on the light source side of the layer.

  Preferred ultraviolet absorbers include benzotriazoles, for example, compounds represented by general formula [III-3] described in JP-A-1-250944, and general formula [III] described in JP-A 64-66646. A compound represented by general formula [I] described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, JP-A No. 4-1633, and JP-A No. 5-165144. The compounds represented by the general formulas (I) and (II) are preferably used.

  These ultraviolet absorbers are used in, for example, high-boiling organic solvents represented by phthalates such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. It is preferable to add in a dispersed manner. Moreover, it is also preferably used to add these ultraviolet absorbers directly to the support. In this case, for example, the embodiment described in JP-T-2004-531611 can also be preferably used.

(Antireflection layer)
When the electromagnetic shielding material roll for electric display of the present invention is used for the purpose of protecting the display screen, it is preferable to provide an antireflection layer.

  The antireflection layer is preferably composed of a plurality of light transmissive layers having different refractive indexes, and more preferably composed of a high refractive index layer, a medium refractive index layer, and a low refractive index layer containing inorganic fine particles. The layers having different refractive indexes are adjusted according to the kind of inorganic fine particles contained therein, the particle diameter, the added amount, the kind of resin binder, and the like. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted so as to be an intermediate value between the refractive index of the base film and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80. The refractive index of the low refractive index layer is preferably 1.46 or less, and particularly preferably 1.3 to 1.45.

  As the antireflection layer, inorganic materials such as metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc., can be used by vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating a thin film in a layer or a multilayer, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin into a single layer or a multilayer can be used.

  In the electromagnetic wave shielding material roll for transparent display of the present invention, when the antireflection layer is formed on the opposite side of the layer having the conductive pattern with the support for the electromagnetic wave shielding material roll for display being sandwiched, After the antireflection layer is formed on the protective film, it is preferable to attach a protective film and then form a conductive pattern layer. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to be reduced. It is preferred to form the layer first. In addition, when the antireflection layer is formed first, it is preferable to form a conductive pattern layer after pasting a protective film in advance from the viewpoint of preventing the layer from being deteriorated by development, plating treatment or the like. .

  As the protective film used in the present invention, a commercially available protective film can be used. From the viewpoint of facilitating coating of a photosensitive silver halide emulsion layer for forming a conductive pattern, the film is used. Is preferably 10 to 100 μm, particularly preferably 20 to 60 μm. If the thickness is less than 10 μm, the rigidity of the film is remarkably reduced, so that the work efficiency of the protection film is likely to be lowered. If the thickness is more than 100 μm, a failure such as a winding reel tends to occur when the film is wound. is there.

  Although there is no restriction | limiting in particular in the kind of adhesive used for a protective film, The thing which does not damage an antireflection film at the time of peeling, without altering an antireflection film is used preferably. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Moreover, as the adhesive force, what is 0.08-0.6N / 25mm is used preferably.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

Example 1
(Preparation of silver halide emulsion)
A silver chlorobromide emulsion (10 mol% silver bromide, 90 mol% silver chloride) was prepared by adding and mixing an aqueous silver nitrate solution and an aqueous potassium bromide and sodium chloride solution while controlling the solution to an aqueous gelatin solution at 35 ° C. did. In this emulsion, potassium rhodium bromide and potassium chloroiridate were added to a concentration of 1.0 × 10 ⁻⁷ (mol / mol silver), and Rh ions and Ir ions were doped. The silver / gelatin mass ratio was 4/1 (silver / gelatin volume ratio was about 0.5), and an alkali-treated low molecular weight gelatin having an average molecular weight of 40,000 was used as the gelatin species. The average particle size was 0.04 μm, and the variation coefficient of the particle size distribution was 0.13.

  Thereafter, 2.0 mg of sodium thiosulfate per mol of silver halide was used for chemical sensitization at 40 ° C. for 80 minutes, and after completion of chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7- The photosensitive silver halide emulsion was obtained by adding 500 mg of tetrazaindene per mole of silver halide and further adding 500 mg of the following sensitizing dye SD-1 per mole of silver halide.

(Support)
On one side of a transparent polyethylene terephthalate film support having a thickness of 120 μm, a width of 60 cm, and a length of 120 m subjected to plasma discharge treatment on both sides, butyl acrylate: styrene: glycidyl acrylate (40:20:40 mass%) latex is An undercoat layer was provided by applying 0.40 g / m ² of hexamethylene-1,6-bis (ethylene urea) to 0.01 g / m ² . On one side, 0.20 g / m ^{2 of} gelatin was applied as a non-photosensitive intermediate layer.

Further, 0.20 g / m ^{2 of} gelatin was coated on the other side as a non-photosensitive intermediate layer.

(Coating of silver halide photosensitive layer)
To the above silver halide emulsion, a surfactant (disulfo oxalate, 2-ethylhexyl, sodium) is added as a coating aid to adjust the surface tension, and a hardener (tetrakis, vinylsulfonylmethyl, methane). Is added at a rate of 20 m so that the silver coating amount is 0.60 g / m ² and the gelatin coating amount is 0.15 g / m ^2. The coating was carried out at a rate of / min and dried to prepare six roll-shaped silver halide photosensitive materials.

(exposure)
The silver halide photosensitive material thus obtained was exposed to the patterns shown in FIGS. 2 (A), (B), 3 and 4. 2A and 2B show the present invention, FIG. 3 shows a comparative example in which the feeding layer is discontinuous, and 4 shows a comparative example in which the feeding layer is continuous. The mesh portion has a lattice shape with a line width of 10 μm and a line interval of 240 μm, and the lattice lines are formed at an angle of 45 degrees with respect to the longitudinal direction of the roll.

  These mesh patterns were exposed using a laser beam having an oscillation wavelength of 440 nm (blue semiconductor laser diode manufactured by Nichia Corporation) while continuously conveying the silver halide photosensitive material.

(Development processing)
The exposed sample is subjected to development processing at 25 ° C. for 60 seconds using an automatic development processing / physical development / plating integrated machine of a leader belt conveyance system with a width of 60 cm, and then the fixing solution described below is applied. A fixing process was performed at 25 ° C. for 120 seconds, followed by a water washing process. Further, after performing physical development at 25 ° C. for 5 minutes using the following physical developer, followed by washing with water, electrolytic plating at 25 ° C. for 5 minutes at 2.5 A / cm ² with the following copper plating solution. Went and washed with water. Finally, it dried with 60 degreeC warm air, and produced the electromagnetic wave shielding material roll body samples 11-13 for a long roll-shaped display. Samples 11 to 14 were produced from exposure of the patterns shown in FIGS. 2 (A), 2 (B), 3 and 4, respectively.

  The electrolytic plating apparatus portion of the automatic development processing / physical development / plating integrated machine has the structure shown in FIG.

(Developer)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1 liter (fixing solution)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to make 1 liter (physical developer)
800ml of pure water
Citric acid 5g
Hydroquinone 7g
Silver nitrate 3g
Add water to bring the total volume to 1 liter (copper plating solution)
125 g of copper sulfate
85 g of sulfuric acid
Polyethylene glycol 0.1g
1mol / L hydrochloric acid 2.0ml
Add water to bring the total volume to 1 liter.

(Evaluation)
The following evaluation was performed with respect to the electromagnetic wave shielding material roll body samples 11 to 14 for displays having a conductive metal mesh portion thus obtained.

<Plating unevenness>
After the plating treatment and drying, the pattern unevenness in the vicinity of the boundary between the shield frame and the mesh part of the sample was photographed at several locations using a high-definition CCD camera and magnified 200 times on a 40-inch monitor screen. And visually observed and evaluated according to the following criteria.

○: No variation in the mesh line width is observed Δ: A slight variation in the mesh line width is observed ×: A portion where the line width is 1/2 or less or a disconnection portion is observed <grounding property>
The shield frame of the roll of electromagnetic shielding material for display and the tin-plated annealed copper conductor having the same width as the shield frame and a thickness of 50 μm are bonded with a heat sealer (160 ° C., 40 N / cm ² , 3 seconds). Resistance was measured at a width of 15 mm and evaluated according to the following criteria.

○: 5Ω or less △: Greater than 5Ω and 20Ω or less ×: Greater than 20Ω

  From Table 1, it can be seen that Samples 11 and 12 of the present invention are display electromagnetic shielding material rolls having excellent panel grounding properties and improved plating unevenness generated during production. The comparative sample 13 had low productivity, and the comparative sample 14 showed uneven plating.

Example 2
2A, 2B, 3 and 4, the conductive mesh pattern, the shield frame, and the power feeding layer are produced with a conductive paste by a printing method, and then plated in the same manner as in Example 1, From the patterns shown in FIGS. 2A, 2 </ b> B, 3 and 4, display electromagnetic wave shielding material roll samples 21 to 24 were produced.

  As a result of evaluation in the same manner as in Example 1, it was found that Samples 21 and 22 of the present invention were excellent in the grounding property of the panel and were electromagnetic wave shielding material rolls for display with improved plating unevenness generated during production. The comparative sample 23 had low productivity, and the comparative sample 24 showed uneven plating.

It is a schematic diagram which shows an example of the electroplating tank suitably used for the plating process of the electromagnetic wave shielding material roll body for a display of this invention. It is a partial top view which shows an example of arrangement | positioning of the mesh pattern and electric power feeding layer in the electromagnetic wave shielding material roll body for displays of this invention. It is a partial top view which shows an example of arrangement | positioning of the mesh pattern and electric power feeding layer in the conventional electromagnetic wave shielding material roll body for a display. It is a fragmentary top view which shows another example of the arrangement | positioning of the mesh pattern in the conventional electromagnetic wave shielding material roll body for a display, and an electric power feeding layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolytic plating apparatus 2 Original fabric roll 3 Roll sheet 4 Transfer roll 5 Water washing tank 6 Electrolytic plating tank 7 Feed roll 8 Electrode plate 9 Electroplating liquid 10 Receiving tank 11 Circulation pump 12 Filter 13 Water washing tank 14 Dryer 15 Electromagnetic wave Shield material roll body 20, 30, 40 Roll sheet 21, 31, 41 Transparent base material 22, 32, 42 Mesh pattern 23, 33, 43 Shield frame 25A, 25B, 35, 45 Feed layer 34, 44 Spacing

Claims (7)

An electromagnetic wave shielding material for a display in which a metal mesh pattern having a screen size of a display is provided on at least one surface of a long transparent base material at regular intervals in the longitudinal direction of the transparent base material and is supplied in a roll state The metal mesh pattern has a conductive mesh pattern and at least a plating layer electroplated thereon, and a shield frame made of a metal mesh or a metal thin film is disposed around the metal mesh pattern. In addition, a power supply layer for electrolytic plating that is in contact with both outer sides in the width direction of the shield frame and whose contact area with the power supply roller changes depending on the position in the longitudinal direction is provided continuously in the longitudinal direction of the transparent substrate. An electromagnetic shielding material roll body for display, characterized by: The electromagnetic wave shielding material roll for display according to claim 1, wherein the power feeding layer is made of a metal thin film or a metal mesh. The electromagnetic wave shielding material roll for display according to claim 1 or 2, wherein a contact area of the power supply layer with the power supply roller is changed by changing a width of the power supply layer. The electromagnetic wave shielding material roll for display according to claim 1 or 2, wherein a contact area of the power supply layer with the power supply roller is changed by changing a mesh pattern of the power supply layer. The electromagnetic shielding material roll for display according to any one of claims 1 to 4, wherein the shield frames on both sides in the longitudinal direction are continuous. 6. The display electromagnetic shielding material according to claim 1, wherein a contact area between the power feeding layer and the power feeding roller is smaller than a central portion of the shield frame around a boundary of the shield frame. Roll body. The display electromagnetic wave according to claim 1, wherein at least a part of the conductive mesh pattern, the shield frame, and the power feeding layer is developed silver produced by a photographic method. Shield material roll body.

Images