JP4972381B2 - Translucent conductive material, manufacturing method thereof, and translucent electromagnetic wave shielding film - Google Patents

Description

The present invention relates to a translucent conductive material. In particular, the present invention relates to a translucent conductive material suitable for a translucent electromagnetic wave shielding film.
In particular, the present invention relates to a translucent conductive material suitable for a translucent conductive electromagnetic wave shielding film for plasma display, which has good visibility and less color unevenness and powder loss.

  In recent years, electromagnetic interference (Electro-Magnetic Interference: EMI) has been rapidly increasing with the increase in the use of various electric facilities and electronic application facilities. EMI has been pointed out to be a cause of malfunction and failure of electronic and electrical equipment, as well as a health hazard to operators of these devices. For this reason, in electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  It is necessary to shield (shield) the electromagnetic wave as a countermeasure against the EMI, but it is obvious that a property that does not allow the metal electromagnetic wave to penetrate may be used. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like are employed. However, in CRT, PDP, etc., it is necessary for an operator to recognize characters and the like displayed on the screen, and thus transparency on the front surface of the display is required. In any of the above methods, the front surface of the display often becomes opaque, and there are many cases that are inappropriate as an electromagnetic wave shielding method applied to a display device.

In addition, since PDP generates a larger amount of electromagnetic waves than CRT or the like, stronger electromagnetic shielding ability is required. For example, a translucent electromagnetic shielding material for CRT has no problem if the surface resistance value is about 300 Ω / sq or less, whereas a translucent electromagnetic shielding material for PDP has no problem with 2.5 Ω / sq or less. A surface resistance value is obtained. In order to satisfy such a requirement for high conductivity, a method of applying an opening pattern to a metal foil having sufficient conductivity by a photolithography technique is used.
However, for example, the copper foil used as the material for forming the shield layer has a metallic luster, so that it reflects light from the outside of the panel, resulting in poor contrast of the screen and a problem that the reflected color of the copper foil is visible. In addition, there is a problem that the light generated from the screen is reflected and the image display quality of the display panel is deteriorated.

It is known that it is effective to blacken the shield layer such as copper foil to effectively prevent both the light generated in the screen, reflection of incident light from the outside, and leakage of electromagnetic waves. Yes.
In particular, as the blackening treatment film of the copper foil for plasma display panel, the surface of the blackening treatment film is uniform and there is no or very little unevenness of the stripe, the etching property is good, and the discoloration with time is Desirably, it is small and the blackened layer is difficult to peel off (excellent adhesion).

Patent Document 1, the zinc surface of the copper foil ^{500~20000μg / dm 2 (0.05~2g / m} 2), black nickel plating layer containing nickel ^{100~500μg / dm 2 (0.01~0.05g / m} 2) and An electromagnetic wave shielding film for a plasma display panel provided is disclosed, and it is said that the surface of the blackening treatment film is uniform and has little unevenness. Patent Document 2 discloses a blackening layer, a conductive pattern layer, In addition, an electromagnetic wave shielding plate having a configuration in which layers are sequentially stacked in the order of the blackening layer is disclosed, and although it has a complicated configuration, generation of moire is suppressed by the multilayered blackening layer. Further, Patent Document 3 discloses a shield material in which visibility is improved by blackening both surfaces and side surfaces of a metal layer pattern to suppress both reflection of outgoing light and incident light. Further, Patent Document 4 discloses an electromagnetic wave shielding filter in which reflected light is suppressed by a blackening layer formed on the surface of a conductive pattern and image contrast is improved. Any of the blackening layers disclosed in Patent Documents 2 to 4 is formed of a mixed phase of nickel and zinc.

Further, Patent Document 5 describes an electromagnetic wave shielding film excellent in visibility by printing a conductive paste having a geometric pattern in which the line width and line interval of a mesh are defined, in which a metal layer is formed on the conductive paste. Alternatively, it is disclosed that the black electrodeposition layer is coated out.
In addition to the electromagnetic wave shielding properties of the electromagnetic wave shielding film, these conventional technologies block reflection, stray light, and external light and improve visibility. However, the uniformity of the film surface accompanying the blackening treatment is still It is not sufficient, and it is desired that there is no unevenness in the surface of the film, and there is no peeling due to powder falling or a micro defect resulting therefrom. In addition, further improvement of the performance of the blackened layer is also required in order to improve visibility.

On the other hand, for the production of electromagnetic shielding films, etc., metal conductive thin films are formed on insulator films with high productivity, such as flexible wiring boards used in electronic devices and electromagnetic shielding films used in plasma displays. Development of forming technology is desired.
For example, Patent Document 6 discloses a method for producing an electromagnetic wave shielding film by exposing and developing a photosensitive material containing a silver salt, and further applying physical development or plating to the developed silver. According to Patent Document 6, it is said that any excellent electromagnetic wave shielding film that can form a fine line pattern more precisely than other methods, and can be mass-produced with high transparency and low cost is obtained.

JP 2004-145063 A Japanese Patent Laid-Open No. 11-266095 JP 2002-9484 A JP 2004-320025 A JP 2001-196784 A JP 2004-221564 A

The present invention has been made in view of the above-mentioned problems, and its purpose is excellent in electromagnetic wave shielding characteristics and good adhesion, and the blackened layer is difficult to peel off. It is to provide a translucent conductive material that has been subjected to a chemical treatment and an electromagnetic wave shielding film for plasma display using the material.
A further object of the present invention is to provide a method for producing a light-transmitting conductive material that is inexpensive and excellent in productivity in addition to the above performance, and a method for producing a light-transmitting electromagnetic wave shielding film with good visibility using a laminated material. Is to provide.

The present invention relates to the following [1] to [8], but other matters are also described for reference.
[1]
In a translucent conductive material having a conductive metal layer formed by patterning a metal part and a visible light transmissive part on a transparent substrate, at least two different alloy compositions are formed on the metal thin wire constituting the metal part. The blackening layer of the layer is laminated, the laminated blackening layer has two or more metal elements including nickel and at least one metal selected from zinc and tin, and the mass of the nickel / other metal A light-transmitting conductive material having a ratio of 0.1 to 50, wherein the mass ratio is gradually decreased from a layer closest to the metal fine wire of the metal portion toward a layer farther away.
[2]
The blackening layer is a two-layer alloy composed of nickel and zinc, and the nickel / zinc mass ratio of the blackening layer on the side close to the fine metal wire is 3 to 15, and the nickel / zinc mass ratio of the blackening layer on the surface layer side Is 0.1-3, The translucent conductive material as described in [1].
[3]
The blackening layer is a two-layer alloy composed of nickel and tin, the nickel / tin mass ratio of the blackening layer on the side close to the fine metal wire is 1 to 2, and the nickel / tin mass ratio of the blackening layer on the surface layer side Is 0.1 to 1, the translucent conductive material according to [1].
[4]
The light-transmitting conductive material according to any one of [1] to [3], wherein the metal part is formed from a pattern including a mesh-like fine line having a line width of 5 μm to 50 μm.
[5]
The light-transmitting conductive material according to any one of [1] to [4], wherein the conductive metal layer contains gelatin.
[6]
The translucent conductive material according to any one of [1] to [5], wherein the translucent conductive material pattern has a conductive metal portion formed by electrolytic plating on the developed silver.
[7]
[1]-[6] The translucent conductive material according to any one of [6], wherein the blackening layer is formed by multi-stage electrolytic plating. Method.
[8]
A translucent electromagnetic wave shielding film comprising the translucent conductive material according to any one of [1] to [6].
The above-described problems of the present invention are achieved by the invention having the following configuration.
1. In a translucent conductive material having a conductive metal layer formed by patterning a metal part and a visible light transmissive part on a transparent substrate, at least two different alloy compositions are formed on the metal thin wire constituting the metal part. A light-transmitting conductive material, characterized by laminating a blackening layer.
2. The laminated blackened layer has two or more metal elements including nickel and at least one metal selected from zinc and tin, and the mass ratio of nickel / other metal is 0.1-50. 2. The translucent conductive material as described in 1 above, which is an alloy, and whose mass ratio decreases sequentially from a layer closest to the metal thin wire of the metal part to a layer far from the metal wire.
3. The blackening layer is a two-layer alloy composed of nickel and zinc, and the nickel / zinc mass ratio of the blackening layer on the side close to the fine metal wire is 3 to 15, and the nickel / zinc mass ratio of the blackening layer on the surface layer side The translucent conductive material as described in 1 or 2 above, wherein is from 0.1 to 3.
4). And said black layer is an alloy of two layers of nickel and tin, nickel / tin weight ratio of the blackened layer on the side closer to the thin metal wires 1-2, nickel / tin weight ratio of the surface layer side of the blackened layer The translucent conductive material as described in 1 or 2 above, wherein is 0.1 to 1.
5. 5. The translucent conductive material as described in any one of 1 to 4 above, wherein the metal part is formed from a pattern including a mesh-like fine line having a line width of 5 μm to 50 μm.
6). 6. The translucent conductive material as described in any one of 1 to 5 above, wherein the conductive metal layer contains gelatin.
7). The translucent conductive material according to any one of the above 1 to 6, which has a conductive metal portion formed by electrolytic plating on developed silver having a pattern of translucent conductive material.
8). 8. The light-transmitting conductive material according to any one of 1 to 7, wherein the blackening layer is formed by multistage electrolytic plating.
9. A translucent electromagnetic wave shielding film comprising the translucent conductive material according to any one of 1 to 7 above.

According to the present invention, the surface of the fine metal wire has high smoothness, good adhesion, and the blackened layer is not easily peeled off. An electroconductive material and an electromagnetic wave shielding film for plasma display using the material can be provided.
In addition to the above performance, the present invention also includes a method for producing a light-transmitting conductive material that is inexpensive and has high productivity, and a method for producing a light-transmitting electromagnetic wave shielding film with good visibility using a general material. Can be provided.
Further, these can be incorporated into a flexible wiring board or a plasma display to improve conductivity and electromagnetic wave shielding performance.
When this translucent electromagnetic wave shielding film is mounted on a plasma television, interference fringes are hardly generated.

The present invention is an invention of a translucent conductive material having a conductive metal layer formed by patterning a metal part and a visible light transmissive part on a transparent substrate, the feature of which is on the conductive metal part And having at least two black layers having different alloy compositions. This multi-layered film layer provides the conductive metal layer with uniform and strong characteristics with less powder loss and defects.
The translucent conductive material of the present invention has a configuration in which fine metal wires constituting a metal portion are laminated with a plurality of black coating layers.
The plurality of (multilayer) black coating layers are each composed of two or more metal elements containing nickel selected from nickel, zinc, and tin, and the mass ratio of the metal other than nickel and nickel (other than Ni / Ni) ) Is an alloy of 0.1 to 50, and the composition is such that the mass ratio decreases sequentially from the film layer closest to the conductive metal to the film layer far from the conductive metal, preventing powder falling and suppressing defects. It is suitable for the purpose of the invention.
Among them, the black layer is a two-layer alloy composed of nickel and zinc, the lower coating layer has a black / nickel / zinc mass ratio of 3 to 15, and the front coating layer has a nickel / zinc mass ratio of 0.1. It is more effective to be ~ 3.
Furthermore, the black layer is a two-layer alloy made of nickel and tin, and the lower coating layer has a black layer nickel / tin mass ratio of 0.3 to 1, and the surface layer side black layer has a nickel / tin mass ratio. It is also effective that it is 0.1-0.3.
In addition, it is preferable that the conductive metal portion is formed from a pattern including a mesh-like thin line having a line width of 5 μm to 50 μm for the purpose of achieving both translucency and conductivity.

In the present invention, the light-transmitting conductive material is obtained by exposing a silver salt photosensitive material in a pattern and developing it, preferably further developing the developed silver by subjecting it to physical development or plating treatment to enhance the conductivity, and then a plurality of black coatings. The manufacturing method for applying the layer is preferable from the viewpoints of cost, productivity, and simplicity. Therefore, the conductive metal layer often contains gelatin derived from a silver salt photosensitive material. This contributes to improving the flexibility of the conductive layer.
In the present invention, the plurality of black coating layers applied on the patterned fine-line developed silver may be subjected to physical development, chemical metal deposition, or any other means as long as the metal thin lines constituting the metal part can be covered. Although it may be coated, it is preferably formed by translucent electroconductive material electroplating, and among them, it is convenient that all of the plurality of black film layers are electroconductive metal parts formed by electroplating.
The translucent conductive material of the present invention has both translucency and electromagnetic shielding properties, and is used for a translucent electromagnetic shielding film. In particular, since the electromagnetic wave shielding property is high, it is suitable as an electromagnetic wave shielding film for plasma display.

The patterned thin metal wire constituting the metal portion of the translucent conductive material of the present invention is not particularly limited as long as it can form the prescribed blackened layer on the surface. For example, some conductive sputtering is applied to the surface of the support (spattered into a pattern or uniformly sputtered and then patterned with a resist), a film provided with a vacuum-deposited thin film, and a copper foil formed into a mesh by etching It is also applied to the metal layer. It is also applicable to a metal pattern formed in a mesh shape by electroless plating and electrolytic plating after printing an electroless plating catalyst such as palladium on a transparent support by a method such as gravure printing or screen printing. . Further, the present invention is also applied to a metal pattern formed in a mesh shape by printing a metal silver particle dispersion on a transparent support and then performing electroplating using the conductivity of the metal silver pattern. Furthermore, the present invention is also applied to a metal pattern formed in a mesh shape by electroplating a conductive silver pattern formed by a silver salt diffusion transfer method.
However, as described above, a developed film obtained by subjecting a silver salt photosensitive material to pattern exposure and development processing, preferably further metal plating treatment is particularly preferable as an application target of the present invention.
The translucent conductive material of the present invention is a film having the above-described silver fine wire or metal-plated silver fine wire mesh pattern, but the metal mesh pattern on the film is continuous (discontinuity in electrical conductivity). Preferably). Any part of the conductive metal layer may be connected, and if the conductive pattern is interrupted, there may be a portion where plating cannot be applied, or a part of the conductive metal layer may become uneven. A conductive metal film is formed on the metal mesh by performing the above plating process on the continuous metal mesh pattern, and the light-transmitting conductive material (conductive film) after the plating process or a functional film carrying the material Is useful, for example, as a printed wiring board formed on an insulator film, an electromagnetic wave shielding film for PDP, or the like.
In general, “mesh” is also used to indicate the density of the sieve mesh. In this specification, “mesh” refers to a mesh-like metal pattern according to a common usage in the industry. Yes.

  As described above, the present invention is most preferably applied to a silver mesh pattern obtained by subjecting a photographic emulsion having a silver salt emulsion layer on a support to a mesh pattern exposure and development treatment. Becomes a solid light-transmitting conductive material without irregularities by the plating treatment of the present invention, which is suitable as a light-transmitting electromagnetic wave shielding film. Therefore, a series of steps for obtaining a light-transmitting electromagnetic wave shielding film from a silver salt emulsion which is the most preferable embodiment of the light-transmitting conductive material of the present invention is described in Patent Document 6 described above.

Next, a method for strengthening conductivity by forming a copper plating layer on a mesh-like silver fine wire pattern of a film using a plating apparatus equipped with an electrolytic plating tank (10 in FIG. 2) described later will be described.
First, a plating solution (15 in FIG. 2) is stored in a plating bath (11 in FIG. 2). In the case of copper plating, examples of the plating solution include a copper plating solution containing one or more of copper sulfate, copper cyanide, copper borofluoride, copper chloride, copper pyrophosphate copper carbonate and the like as a copper supply source compound. It is preferable to use a plating solution containing copper sulfate from the viewpoint that the bathing cost is low and management is easy, and it is more preferable to use a copper sulfate pentahydrate or a copper sulfate aqueous solution previously dissolved in water.
In the copper plating solution, the copper ion source other than the above can be used without particular limitation as long as it is a copper compound that can be dissolved in an ordinary acidic solution and can form an acidic copper plating solution having a pH of 3 or lower. Specific examples of the copper ion source other than the above include copper oxide, copper methanesulfonate, copper alkanesulfonate such as copper propanesulfonate, copper alkanol sulfonate such as copper propanolsulfonate, copper acetate, copper citrate, Examples include organic acid copper such as copper tartrate and salts thereof. A copper compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The copper ion concentration in the copper plating solution is preferably in the range of 150 to 300 g / L, more preferably in the range of 150 to 250 g / L, and even more preferably in terms of the mass of copper sulfate pentahydrate. The range is 180-220 g / L.
Usually, when electrolytic plating is performed, the copper ion concentration in the plating solution is often 80 to 100 g / L. However, when electrolytic plating is performed on a film having a high surface resistance as in the present invention, electrons are difficult to spread over a large area, so that the current density per unit area is high, and the supply of electrons is performed at a copper ion concentration within a normal range. On the other hand, the supply of copper ions cannot catch up, hydrogen is generated on the film surface, and poor-quality copper plating (so-called “burn”) adheres, making it difficult to uniformly form a plating film without unevenness. Therefore, in the present invention, the copper ion concentration of the plating solution is preferably 150 g / L or more, and the occurrence of this “burn” can be prevented, and a uniform and non-uniform plating film can be formed.
It should be noted that the copper ion concentration within a preferable range of 300 g / L or less is uneconomical even if it is used in excess of 300 g / L, is uneconomical, takes time for dissolution, and tends to precipitate. This is because of such problems.

  The acid added to the plating solution is not particularly limited as long as the pH of the plating solution is kept sufficiently low, and examples thereof include sulfuric acid, nitric acid, hydrochloric acid and the like. The pH varies depending on the acid concentration, but is preferably 3 or less, more preferably 1 or less. In addition, since it becomes easy to precipitate copper when an acidic copper plating solution exceeds pH 3, it is not preferable.

  For example, when a plating solution containing copper sulfate is used, the concentration of sulfuric acid in the plating solution is preferably 30 to 300 g / L, and more preferably 50 to 150 g / L. The pH varies depending on the sulfuric acid concentration, but is preferably 3 or less, more preferably 1 or less.

It is preferable that chlorine ions exist in the copper plating solution, and the concentration thereof is preferably 20 to 150 mg / L, more preferably 30 to 100 mg / L.
Next, an organic additive added to the copper plating solution will be described. Organic additives include organic compounds that suppress plating reactions (plating inhibitors), organic compounds that promote plating reactions (plating accelerators), and organic compounds that flatten the tribe film that is electrodeposited during plating. It is preferable to contain at least one compound selected from these, more preferably a combination of two or more, and particularly an organic compound that suppresses the plating reaction, and an organic compound that promotes the plating reaction It is most preferable to add all of the organic compounds that flatten the plating growth in combination.

As the organic compound that suppresses the plating reaction, a chain polymer component having a water-soluble group is preferable. The chain polymer may be branched. In addition, the polymer may be composed of a single monomer or a copolymer of two or more monomers. The water-soluble group is preferably a hydroxyl group, a sulfate group, a sulfite group, a carboxyl group, or a phosphonic acid group, and particularly preferably a hydroxyl group. Especially as a polymer component, the polymer component which has an oxygen atom tends to adsorb | suck to a copper plating surface, and suppresses plating reaction. It is preferable because the plating is uniformly dense because it is easily adsorbed to the outside of the hole where the plating reaction has proceeded excessively and is selectively suppressed.
As the polymer component, polyalkylene glycols are preferable. In this case, the alkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 3 carbon atoms. Specifically, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block copolymer (pluronic) surfactant, polyethylene glycol / polypropylene glycol graft copolymer (tetronic) surfactant, glycerin ether, dialkyl A compound selected from the group consisting of ethers can be used, preferably polyethylene glycol having a molecular weight of 10,000 to 10000, more preferably 2000 to 6000, polypropylene glycol having a molecular weight of 100 to 5000, more preferably 200 to 2000, molecular weight of 1,000 to 10,000. More preferably, a polyethylene glycol / polypropylene glycol block copolymer of 1500 to 4000 is mentioned, and 2000 to 6 00 polyethylene glycol is most preferred. In addition, the chain polymer polymer component which has a water-soluble group can be used 1 type or in combination of 2 or more types. As a density | concentration of a polymer component, 10-5000 mg / L is preferable and 50-2000 mg / L is more preferable.

  As the compound that accelerates the plating reaction, a system organic compound having a sulfur-containing group is preferable. Examples of the sulfur-containing group include sulfide groups, thiol groups (mercapto groups), sulfonic acid groups, sulfinic acid groups, and thiosulfuric acid groups. By including a sulfur-based organic compound having a sulfur-containing group, the concave portions that are difficult to be plated are efficiently turned to promote the reaction, so that the plating becomes uniform and dense, and the scratch resistance, heat resistance, and the like are improved. Specific examples of the sulfur-based organic compound having a sulfur-containing group include a sulfoalkylsulfonic acid (the alkyl group has 1 to 10 carbon atoms, preferably 2 to 4) and a salt thereof, a bissulfo organic compound, and a dithiocarbamic acid derivative. A compound selected from thiosulfuric acid or a salt thereof can be used, and preferred specific examples include bis (3-sulfopropyl) disulfide (SPS), sodium mercaptopropanesulfonate (MPS) and the like. In addition, it is also preferable to use the compounds listed in paragraph [0012] of JP-A-7-316875. In addition, you may use a sulfur type organic compound 1 type or in combination of 2 or more types. As a density | concentration of a sulfur type organic compound, 0.02-2000 mg / L is preferable and 0.1-300 mg / L is more preferable.

Further, a nitrogen compound is preferable as the organic compound for flattening the metal growth film electrodeposited in the plating process. By containing a nitrogen compound in the plating solution, the inhibitory organic compound is more diffusion-controlled by using it in conjunction with the organic compound agent that preferably suppresses the plating reaction described above, thereby making it mesh-like. By selectively adsorbing outside the pattern hole, plating is suppressed, and the uniformity of the plating thickness is improved.
As the nitrogen compound, polyalkyleneimine, 1-hydroxyethyl-2-alkylimidazoline salt, polydialkylaminoethyl acrylate quaternary salt, polyvinylpyridine quaternary salt, polyvinylamidine, polyallylamine, polyaminesulfonic acid, auramine and derivatives thereof, A compound selected from the group consisting of methyl violet and derivatives thereof, crystal violet and derivatives thereof, Janus black and derivatives thereof, and Janus green can be used. In addition, a nitrogen compound can be used 1 type or in combination of 2 or more types. As a density | concentration of a nitrogen compound, 0.1-1000 mg / L is preferable and 0.5-150 mg / L is more preferable.

When the copper plating process is composed of two or more stages, the organic additive concentration in the latter half copper plating solution is preferably 70% or less with respect to the organic additive concentration added to the first half copper plating solution. More preferably, it is 50% or less, and most preferably it does not contain substantially. “Substantially not containing” means that the solution is not positively and intentionally added except that the liquid is brought in from the pre-bath by processing and is mixed minutely.
The sum of the total number of copper plating tanks is preferably 2 to 40 tanks, more preferably 4 to 30 tanks, and particularly preferably 10 to 20 tanks. The ratio of the number of tanks in the latter half to the first half of the copper plating solution is preferably 0.5 to 2.0.
The bath temperature of the copper plating solution is preferably 15 to 40 ° C, particularly preferably 20 to 35 ° C.

  The stirring method for the copper plating solution is not particularly limited as long as commonly used aeration, ultrasonic stirring, or the like is used. Moreover, as temperature of the water for washing after copper plating, 15-40 degreeC is preferable and 20-30 degreeC is especially preferable.

  The surface resistance of the film immediately before the electrolytic plating is preferably 1 to 1000Ω / □, more preferably 5 to 500Ω / □, and still more preferably 10 to 100Ω / □.

The applied voltage is preferably in the range of 1 to 100V, more preferably in the range of 2 to 60V. When a plurality of electrolytic plating tanks are installed, it is preferable to lower the applied voltage of the electrolytic plating tank stepwise. Moreover, as an electric current amount by the side of the entrance of the 1st tank, 1-30A is preferable and 2-10A is more preferable.
The power supply rollers 12a and 12b are preferably in contact with the entire surface of the film (the portion of the contact area that is substantially in electrical contact is 80% or more).

  The thickness of the conductive metal portion plated by the electrolytic plating treatment is preferable because the viewing angle of the display is increased as the thickness of the electromagnetic shielding material for the display is reduced. Furthermore, as a use of the conductive wiring material, a thin film is required because of a demand for high density. From such a viewpoint, the thickness of the shield film made of the plated conductive metal is preferably less than 9 μm, more preferably from 0.1 μm to less than 5 μm, and from 0.1 μm to less than 3 μm. More preferably.

  Moreover, in the plating process of this invention, if the surface resistance of the film just before performing said electroplating process is a film of 1-1000 ohms / square, you may perform an electroless-plating process before that.

  Moreover, it is preferable that the electroconductive pattern on a film is continuous (it is not interrupted electrically). It is only necessary to be partially connected, and if the conductive pattern is interrupted, there is a possibility that a portion where plating cannot be applied in the first electrolytic plating tank may be formed or uneven.

  The plating rate during the plating process can be performed under moderate conditions, but high-speed plating of 5 μm / hr or more is also possible. In the plating process, from the viewpoint of improving the stability of the plating solution, for example, various additives such as a ligand such as EDTA can be added to the plating solution and used.

Next, the antirust treatment preferably applied to the electromagnetic wave shielding film and the antirust agent contained in the film by the treatment will be described.
In the present invention, the rust preventive agent preferably contained in the electromagnetic wave shielding film may be contained in a photosensitive material (for example, in an emulsion layer or in a surface protective coarse) which is a material for producing a shielding film. The material may be contained in a developer, a fixing solution, or a stabilizer when developing after pattern exposure, and may be incorporated into a shield film during processing, or an electroplating solution or electroless after development It may be contained in a plating solution, an oxidizing solution, or an independent rust preventive bath and taken into the shield film during processing. In particular, it is most preferable to immerse the rust preventive agent in the film by dipping in a rust preventive bath after the blackening treatment described later.

As a rust preventive agent used for this invention, a nitrogen-containing heterocyclic compound and an organic mercapto compound are preferable, and a nitrogen-containing heterocyclic compound is used preferably especially.
Preferable examples of the nitrogen-containing organic heterocyclic compound are 5- or 6-membered azoles, and 5-membered azoles are particularly preferable. As the rust preventive agent used in the present invention, a nitrogen-containing organic heterocyclic compound or an organic mercapto compound is preferably used and used. These rust inhibitors can be used alone or in combination of two or more, and the preferred adsorption amount of the rust inhibitor is 0.01 to 0.5 g / m ² , particularly preferably 0.03 to 0.3 g / m ² . is there.

The blackening treatment according to the present invention is a treatment for electrodepositing two or more layers of a mixed film containing at least nickel on the surface of the conductive metal and containing a metal selected from zinc and tin. In this configuration, the mass ratio gradually decreases from the near blackened layer to the far layer. When viewed from the mesh surface side, the black layer closest to the conductive metal surface is represented as the lower layer side, and the far black layer is represented as the surface layer side.
Ni / other metal mass ratio is 0.1 to 50, preferably 0.1 to 15 and a blackening layer having a smaller mass ratio on the surface layer side than the mass ratio on the lower layer side is provided. Done. The other metal species is preferably zinc or tin. In the case of zinc, the lower layer side Ni / Zn mass ratio is in the range of 3 to 15, and the surface layer side Ni / Zn mass ratio is in the range of 0.1 to 3. In the case of tin, the lower layer is in the lower layer. It is preferable that the blackening layer is provided in a range where the side Ni / Sn mass ratio is 0.3 to 1 and the surface side Ni / Sn mass ratio is 0.1 to 0.3.

In the present invention, when at least two or more blackening layers are coated on a thin metal wire, a plurality of electrolytic baths are used to convey a sample to be processed (developed photosensitive material), an electrolytic solution composition, an electrolytic solution temperature, A method of performing electrolytic treatment while sequentially moving a plurality of tanks whose applied voltage conditions are changed is excellent in terms of ease of processing condition control and productivity. FIG. 1 described later is a schematic diagram of a typical example of an electrolytic cell for blackening treatment and electrolytic plating treatment.
The metal compound used for the treatment can be used by appropriately combining various salts such as sulfate, nitrate and chloride. In addition to these metal compounds, various stabilizers such as ammonia, EDTA, thiocyanate or pyrophosphate that enhance the stability of the plating solution, brighteners such as naphthalene sulfonate and saccharin, sodium lauryl sulfate as a pit inhibitor It is also possible to add surfactants such as those described above, plating suppression, acceleration or smoothing agents as described above.

The preferred pH of the blackening treatment liquid varies depending on the combination of metal species, but it is usually preferred to treat at a constant pH while correcting the pH with an acid or alkali for the purpose of controlling the stability and reactivity of the liquid. Moreover, the method of obtaining the effect similar to pH correction | amendment can also be used suitably by using together buffering agents, such as a succinic acid and a citric acid, and suppressing pH fluctuation | variation.
The preferable temperature of the blackening treatment liquid is 30 to 60 ° C, more preferably 38 to 50 ° C. The stirring of the liquid is preferably carried out by well-known air stirring, jet stirring for jetting the liquid from a small nozzle, or a method of stirring by circulating the tank liquid.

Nickel, carbon, or the like can be used as an anode electrode for blackening treatment, but it is preferable to use a carbon electrode in order to form a blackened layer having a stable mass ratio. In this case, the concentration of nickel and zinc decreases as a result of the blackening treatment, but a blackening treatment is carried out while replenishing by making up a replenisher that adds the amount reduced by electrodeposition so that it is always constant. Is preferred.
The current density per minute on the cathode surface of the blackening treatment is 0.1 to 5 A / dm ² , preferably 0.3 to 3 A / dm ² . In the case of continuous blackening treatment, the linear velocity is preferably from 0.1 to 30 m / min, particularly preferably from 0.5 to 10 m / min.
In the case of using a plurality of electrolytic cells, the number of blackening treatment tanks is preferably 2 to 5 tanks, more preferably 2 to 3 tanks from the viewpoint of ease of processing, cost, and the like.

<Electrolytic treatment equipment>
The blackening treatment according to the present invention is preferably performed in combination with an electrolytic plating treatment on developed silver as a preceding stage. An electrolytic processing apparatus for reinforcing a series of fine metal wires including electrolytic plating and blackening processing and improving visibility on a developed photosensitive material will be described with reference to conceptual diagrams.

In the present invention, it is appropriate to use a multi-tank electrolysis apparatus for the film on which the silver mesh pattern is formed by the above treatment. The structure of the multi-stage tank of the electroplating / blackening treatment apparatus having a multi-tank structure shown in FIG. 1 is shown, and each tank corresponds to an electrolytic plating / blackening treatment / rust prevention treatment process to be described later. FIG. 2 shows a configuration of one electrolytic cell of a multi-tank apparatus for the purpose of explanation. The blackening treatment tank is an electrolytic cell having substantially the same functional tank as the electrolytic plating tank 10, The blackening treatment tank is configured so as to follow a treatment process described later.
The conceptual diagram of the structure of the apparatus which performs a series of bathing processes, such as the electrolytic plating process shown in FIG. 1, a blackening process, and a rust prevention process, is further described. The upstream processes such as tanks a and b are tanks used in the electroplating process, and multi-stage electroplating is performed using a plurality of layers, so that fine control of the electrolysis conditions is possible and a high quality electrodeposition film is obtained. Be convenient.
A blackening process is performed following the electrodeposition process. In the blackening treatment, a plurality of blackened layers having different metal mass ratios of the blackened film are electrodeposited by using a plurality of tanks. Although the operation control conditions such as the treatment liquid composition and voltage application conditions in the tank are changed, it is convenient that the function and configuration of the tank are the same as those of the electroplating tank.
FIG. 2 shows a first tank as an example of the electrolytic cell of the continuous processing system shown in FIG. In FIG. 2, after the copper plating solution is stored in the electrolytic plating tank 11, the film 16 is set in a state where it is wound around a supply reel (not shown), and the surface of the film 16 on which the plating is to be formed is the feeding roller. The film 16 is wound around a conveyance roller (not shown) so as to come into contact with 12a and 12b. A pair of anode plates 13 are disposed in parallel in the plating bath 11, and a pair of guide rollers 14 are disposed inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13. The guide roller 14 can move in the vertical direction, thereby adjusting the plating processing time of the film 16.

  Above the plating bath 11, a pair of feed rollers (cathodes) 12 a and 12 b for guiding the film 16 to the plating bath 11 and supplying current to the film 16 are rotatably arranged. A liquid draining roller 17 is rotatably disposed above the plating bath 11 and below the outlet-side power supply roller 12b. Between the liquid draining roller 17 and the outlet-side power supply roller 12b. Is provided with a spray for water washing (not shown) for removing the plating solution from the film.

In the electrolytic plating tank 10 described above, for example, when the size of the electrolytic plating tank is 10 × 10 × 10 cm to 100 × 200 × 300 cm, the lowermost portion of the surface where the feeding roller 12a on the entrance side and the film 16 are in contact with each other The distance (distance La shown in FIG. 1) between the surface and the plating solution is preferably 0.5 to 15 cm, more preferably 1 to 10 cm, and even more preferably 1 to 7 cm. Moreover, it is preferable that the distance (distance Lb shown in FIG. 1) between the lowermost part of the surface where the power supply roller 12b on the outlet side and the film 16 are in contact with the plating solution surface is 0.5 to 15 cm.
A voltage is applied to the anode plate 13 and the power supply rollers 12a and 12b, and the film 16 is conveyed while being in contact with the power supply rollers 12a and 12b. The film 16 is introduced into the electrolytic plating tank 11 and immersed in the copper plating solution 15 to perform copper plating. When passing between the liquid removal rollers 17, the copper plating solution 15 adhered to the film 16 is wiped off and collected in the electrolytic plating tank 11.
The film 16 is washed with water and wound on a take-up reel (not shown) after all the plating processes are completed or each time each plating process is completed.

  The conveyance speed of the film 16 is preferably set in the range of 0.5 m / min to 30 m / min. The conveyance speed of the film 16 is more preferably in the range of 1 m / min to 10 m / min.

In the case of copper plating, the applied voltage is preferably in the range of 1V to 100V, more preferably in the range of 2V to 60V. It is preferable that the applied voltage in the electrolytic plating tank is gradually lowered toward the traveling direction of the film. The amount of current in the first tank is preferably 1A to 30A, and more preferably 2A to 10A.
The power supply rollers 12a and 12b are preferably in contact with the entire surface of the film (the portion of the contact area that is substantially in electrical contact is 80% or more).

  It is preferable to cool the power supply rollers 12a and 12b and the film 16 by providing a shower or the like in the vicinity of the power supply rollers 12a and 12b and the film between the power supply rollers 12a and 12b and the surface of the plating solution.

  In addition, it is preferable to perform water washing and acid washing before performing a plating process in the said electrolytic plating tank. As the treatment liquid used for the acid cleaning, one containing sulfuric acid or the like can be used.

Translucent electromagnetic shielding film / optical filter
As described above, a light-transmitting conductive material having a blackened silver mesh pattern obtained by exposing, developing, plating, and blackening a photosensitive material containing a silver salt emulsion can be obtained.
Since this translucent conductive material has high electromagnetic shielding properties and translucency, CRT, EL, liquid crystal display, plasma display panel, other image display grat panels, or imaging semiconductors represented by CCD It can be used as a light-transmitting electromagnetic wave shielding film by being incorporated in an integrated circuit or the like. In addition, the use of the translucent conductive material according to the present invention is not limited to the display device and the like, but a measurement device that generates an electromagnetic wave, a window or a case for looking inside the measurement device or the manufacturing device, a radio wave, and the like. It can be provided in a window of a building or a window of an automobile that may be damaged by electromagnetic waves due to a tower, a high voltage line, or the like.

  In the translucent conductive material according to the present invention, the silver mesh is formed of developed silver, the conductivity is enhanced by plating, and the visibility is improved by blackening. Therefore, since the fine line pattern is precise and the image quality can be maintained or improved without significantly impairing the brightness, it is particularly useful as a translucent electromagnetic shielding film used on the front surface of an image display device such as a plasma display panel. .

In order to prevent the electromagnetic wave shielding ability of the translucent electromagnetic shielding film made of the translucent conductive material from being lowered, it is desirable to ground the conductive metal part. For this reason, it is desirable to form a conductive part for grounding on the translucent electromagnetic wave shielding film, and to make the conductive part electrically contact the ground part of the display body. The conducting portion is preferably provided around the metallic silver portion or the conductive metallic portion along the peripheral edge portion of the translucent electromagnetic shielding film.
The conductive part may be formed by a mesh pattern, or may not be patterned, for example, may be formed by a solid metal foil, but in order to improve electrical contact with the ground part of the display body, It is preferable that it is not patterned like a metal foil solid.

  Moreover, when using the translucent conductive material of this invention as a translucent electromagnetic wave shielding film, an adhesive layer, a glass plate, a protective film and a function described later are used for the translucent conductive film (translucent electromagnetic wave shielding film). It is preferable to attach an adhesive film or the like to form an optical film. Hereinafter, each layer that can be provided on the translucent conductive film (translucent electromagnetic wave shielding film) will be described.

<Adhesive layer>
The position where the adhesive layer is provided on the translucent electromagnetic wave shielding film may be the surface on the side where the conductive metal portion is formed, or the surface opposite to the side where the conductive metal portion is formed. You may form in the bonding part of a translucent electromagnetic wave shielding film and other layers (a glass plate, a protective film, a functional film, etc.). The thickness of the adhesive layer is preferably equal to or greater than the thickness of the metal silver part (or conductive metal part), and can be, for example, in the range of 10 to 80 μm, and more preferably 20 to 50 μm.

  The refractive index of the adhesive in the adhesive layer is preferably 1.40 to 1.70. By setting the refractive index to 1.40 to 1.70, the difference between the refractive index of the support of the translucent electromagnetic wave shielding film and the refractive index of the adhesive is reduced, and the visible light transmittance is prevented from being lowered. be able to.

The adhesive is preferably an adhesive that flows by heating or pressurization, and particularly exhibits fluidity by heating at 200 ° C. or less or pressurization by 1 kgf / cm ² (0.1 MN / m ² ) or more. An adhesive is preferred.
By using such an adhesive, the translucent electromagnetic wave shielding film can be adhered to a display or a plastic plate, which is an adherend, by flowing the adhesive layer. It can be easily bonded to an adherend having a curved surface or a complicated shape by molding.
For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the light-transmitting electromagnetic wave shielding film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or more, and most preferably 80 to 120 ° C. in view of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poise (10 ³ MPa · s) or less, and normally, the flow is recognized within about 1 to 10 seconds at that temperature.

  Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.459), polyvinyl butyl ether (n = 1.456) Ethers, polyesters such as polyvinyl acetate (n = 1.467), polyvinyl propionate (n = 1.467), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55) ), Polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 to 1.6), polyethyl acrylate (n = 1.469), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463) , Poly-t-butyl acrylate (n = 1.464), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethylene (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl Methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.475), poly-n-propyl methacrylate (n = 1.484), poly-3,3,5-trimethylcyclohexyl methacrylate ( n = 1.484), polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.487), poly-1,1-diethylpropyl methacrylate (n = 1.485). 489) and poly (meth) acrylic acid esters such as polymethyl methacrylate (n = 1.489) can be used. Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used.

Further, copolymer resins other than acrylic resin and other than acrylic include epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1.49), polyester acrylate (n = 1.48 ~ 1.54) can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule such as epoxy acrylate is effective for improving the adhesion. These copolymer resins can be used in combination of two or more as required.
On the other hand, the mass average molecular weight of the adhesive polymer (measured using a standard polystyrene calibration curve by gel permeation chromatography, hereinafter the same) is preferably 500 or more. When the molecular weight is 500 or less, the cohesive force of the adhesive composition is too low, and the adhesion to the adherend may be reduced.

  The adhesive can contain a curing agent (crosslinking agent). As the curing agent for the adhesive, amines such as triethylenetetramine, xylenediamine, diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more.

The addition amount of the curing agent is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the adhesive polymer. If the added amount is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesiveness.

In addition to the hardener, additives such as diluents, plasticizers, antioxidants, fillers, colorants, UV absorbers and tackifiers may be added to the adhesive as necessary. Also good.
In order to form an adhesive layer on the translucent electromagnetic wave shielding film, a part or the whole surface of the conductive metal part is coated with the adhesive layer composition containing the above-mentioned adhesive polymer, curing agent, and other additives. It can form by apply | coating so that it may carry out, solvent drying, and heat-hardening.

<Protective film>
A protective film can be attached to the translucent electromagnetic wave shielding film according to the present invention. The protective film may be provided on both sides of the transmissive electromagnetic wave shielding film, or may be provided only on one side (for example, on the conductive metal portion).
As described later, the translucent electromagnetic wave shielding film is often further bonded with a functional film having effects such as reinforcing the outermost surface, imparting antireflection properties, imparting antifouling properties, etc. When providing a conductive film on a translucent electromagnetic wave shielding film, it is desirable to peel off the protective film. Therefore, it is desirable that the protective film be peelable.
The peel strength of the protective film is preferably 5 mN / 25 mm width to 5 N / 25 mm width, more preferably 10 mN / 25 mm width to 100 mN / 25 mm width. If it is less than the lower limit, peeling is too easy and the protective film may peel off during handling or inadvertent contact, which is not preferable, and if it exceeds the upper limit, a large force is required for peeling, and at the time of peeling, The mesh-shaped metal foil may peel off from the transparent base film (or from the adhesive layer), which is also not preferable.

  As the film constituting the protective film, it is preferable to use a resin film such as a polyolefin resin such as polyethylene resin or polypropylene resin, a polyester resin such as polyethylene terephthalate resin, a polycarbonate resin, or an acrylic resin. Moreover, it is preferable to perform the corona discharge process on the bonding surface of a protective film, or to laminate | stack an easily bonding layer.

<Functional film>
When using a translucent electromagnetic wave shielding film for a display (especially a plasma display), it is preferable to give each functionality by sticking the functional film which has the functionality demonstrated below. The functional film can be attached to the translucent electromagnetic wave shielding film through an adhesive or the like.

(Anti-reflection and anti-glare properties)
The translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, or anti-glare (AG: anti-glare) properties to prevent the reflection of mirror images, or both characteristics. It is preferable to provide any of the antireflection antiglare (ARAG) properties provided.
With these performances, it is possible to prevent the display screen from becoming difficult to see due to the reflection of a lighting fixture or the like. Further, by reducing the visible light reflectance of the film surface, not only the reflection can be prevented but also the contrast and the like can be improved. When the functional film having antireflection properties and antiglare properties is attached to the translucent electromagnetic wave shielding film, the visible light reflectance is preferably 2% or less, more preferably 1.3% or less, and still more preferably Is 0.8% or less.

The functional film as described above can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate.
As the antireflection layer, for example, a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, a thin film of silicon oxide, or the like formed as a single layer with an optical film thickness of, for example, a quarter wavelength, a different refractive index, It may be formed of a multi-layered laminate of thin films of inorganic compounds such as metal oxides, fluorides, silicides, nitrides, sulfides, or organic compounds such as silicon resins, acrylic resins, and fluorine resins. it can.

The antiglare layer can be formed from a layer having a minute uneven surface state of about 0.1 μm to 10 μm. Specifically, acrylic, silicon-based resin, melamine-based resin, urethane-based resin, alkyd-based resin, fluorine-based resin and other thermosetting or photo-curable resins, silica, organosilicon compounds, melamine, acrylic, etc. It is possible to form by coating and curing an ink in which particles of the inorganic compound or organic compound are dispersed. The average particle size of the particles is preferably about 1 to 40 μm.
The antiglare layer can also be formed by applying the thermosetting or photocurable resin and pressing and curing a mold having a desired gloss value or surface state.
When the antiglare layer is provided, the haze of the translucent electromagnetic wave shielding film is preferably 0.5% or more and 20% or less, more preferably 1% or more and 10% or less. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the clarity of the transmitted image tends to be low.

(Hard coat property)
In order to add scratch resistance to the translucent electromagnetic wave shielding film, it is also preferable that the functional film has a hard coat property. Examples of the hard coat layer include acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, thermosetting resins such as fluorinated resins, and photocurable resins. There is no particular limitation. The thickness of the hard coat layer is preferably about 1 to 50 μm. When the above-mentioned antireflection layer and / or antiglare layer is formed on the hard coat layer, a functional film having scratch resistance, antireflection property and / or antiglare property is obtained, which is preferable.
As for the surface hardness of the translucent electromagnetic wave shielding film to which the hard coat property is imparted, the pencil hardness according to JISK-5400 is preferably at least H, more preferably 2H, and further preferably 3H or more.

(Antistatic property)
In order to prevent dust adhesion due to electrostatic charging and electrostatic discharge due to contact with the human body, it is preferable that the transmissive electromagnetic wave shielding film has antistatic properties.
As the functional film having antistatic properties, a film having high electrical conductivity can be used. For example, the electrical conductivity may be about 10 ¹¹ Ω / □ or less in terms of surface resistance.
A highly conductive film can be formed by providing an antistatic layer on a transparent substrate. Specific examples of the antistatic agent used in the antistatic layer include a trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), a trade name of electro slipper (manufactured by Kao Corporation), and the like. In addition, the antistatic layer may be formed of a known transparent conductive film such as ITO, or a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. Antistatic properties may be imparted to the hard coat layer, antireflection layer, antiglare layer and the like by adding conductive fine particles.

(Anti-fouling property)
It is preferable that the light-transmitting electromagnetic wave shielding film has antifouling property because it can be easily removed when the fingerprint is prevented from being smudged or smudged.
The functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate. The compound having antifouling property may be a compound having non-wetting properties with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin), and examples of the silicon compound include trade name Takata Quantum (manufactured by Nippon Oil & Fats Co., Ltd.).

(UV-cutting property)
The translucent electromagnetic wave shielding film is preferably imparted with UV-cutting properties for the purpose of preventing deterioration of a dye and a transparent substrate described later. The functional film having ultraviolet cut-off property can be formed by a method in which the transparent substrate itself contains an ultraviolet absorber or by providing an ultraviolet absorbing layer on the transparent substrate.
As the ultraviolet ray cutting ability necessary for protecting the dye, the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less. A functional film having an ultraviolet cutting property can be obtained by forming on a layer transparent substrate containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays. Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their types and concentrations are dispersibility / solubility in the medium to be dispersed or dissolved, absorption wavelength / absorption coefficient, thickness of the medium. It is determined from the above and is not particularly limited.

In addition, it is preferable that the functional film which has ultraviolet-cutting property has little absorption of visible light region, and does not show visible light transmittance | permeability remarkably or exhibit colors, such as yellow.
Moreover, when the layer containing the pigment | dye mentioned later is formed in the functional film, it is desirable for the layer which has ultraviolet-ray cutting property to exist outside the layer.

(Gas barrier properties)
If a translucent electromagnetic shielding film is used in a temperature / humidity environment higher than room temperature and humidity, the pigments described later deteriorate due to moisture, or moisture aggregates in the adhesive used for bonding and the bonding interface and becomes cloudy. In other cases, the translucent electromagnetic wave shielding film preferably has a gas barrier property because the adhesive may be phase-separated due to the influence of moisture and may precipitate and become cloudy.
In order to prevent such deterioration and fogging of the pigment, it is important to prevent moisture from entering the pigment-containing layer and the adhesive layer, and the water vapor permeability of the functional film is 10 g / m ² · day or less, Preferably it is 5 g / m ² · day or less.

(Other optical properties)
Since a plasma display generates intense near-infrared rays, it is preferable to impart infrared shielding properties (particularly near-infrared shielding properties) when a light-transmitting electromagnetic wave shielding film is used particularly for plasma displays.
As a functional film which has near-infrared cut property, what has the transmittance | permeability in a wavelength range 800-1000 nm is 25% or less, More preferably, it is 15% or less, More preferably, it is 10% or less.

  Moreover, when using a translucent electromagnetic wave shielding film for a plasma display, it is preferable that the transmitted color is neutral gray or blue gray. This is because the light emission characteristics and contrast of the plasma display are maintained or improved, and white having a slightly higher color temperature than standard white may be preferred.

  Furthermore, the color plasma display is not in a state where the color reproducibility is sufficiently satisfied. In particular, the emission spectrum of red display shows several emission peaks ranging from a wavelength of about 580 nm to about 700 nm. There is a problem that red emission becomes poor in color purity close to orange due to a strong short wavelength emission peak. Therefore, the functional film preferably has a function of selectively reducing unnecessary light emission from the phosphor or the discharge gas which is the cause of the functional film.

  These optical properties can be controlled by using a dye. In other words, a near-infrared absorber is used for near-infrared cut, and a dye that selectively absorbs unnecessary luminescence can be used to reduce unnecessary luminescence. The color tone can also be made suitable by using a dye having appropriate absorption in the visible region.

  As the coloring matter, a general dye or pigment having a desired absorption wavelength in the visible region and a compound known as a near infrared absorbing agent can be used, and the type thereof is not particularly limited. , Phthalocyanine, methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, pyromethene, dithiol Examples thereof include organic dyes that are generally commercially available, such as compounds and diiminium compounds.

Since the temperature of the panel surface of the plasma display is high and the temperature of the translucent electromagnetic wave shielding film rises when the temperature of the environment is high, it is preferable that the dye has heat resistance that does not deteriorate at, for example, about 80 ° C. is there.
In addition, some dyes have poor light resistance, but if such dyes are used to cause problems with light emission of plasma displays and deterioration of external light by ultraviolet rays or visible rays, a functional film as described above. It is preferable to prevent the dye from being deteriorated by ultraviolet rays or visible rays by adding an ultraviolet absorber or providing a layer that does not transmit ultraviolet rays.
The same applies to humidity and a combined environment in addition to heat and light. When it deteriorates, the transmission characteristics of the optical filter change, and the color tone may change or the near-infrared cutting ability may decrease.
Further, in order to dissolve or disperse in a resin composition for forming a transparent substrate or a coating composition for forming a coating layer, the dye preferably has high solubility and dispersibility in a solvent.

The concentration of the dye can be appropriately set from the absorption wavelength / absorption coefficient of the dye, the transmission characteristics / transmittance required for the translucent electromagnetic wave shielding film, and the type / thickness of the medium or coating film to be dispersed. .
When making a functional film contain a pigment | dye, you may contain in the inside of a transparent base material, and you may coat the layer containing a pigment | dye on the base-material surface. Moreover, you may contain a pigment | dye in an adhesive layer. Further, two or more kinds of dyes having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing dyes may be included.

  In addition, since the dye may be deteriorated by contact with metal, when such a dye is used, the functional film containing the dye has a conductive layer on the translucent electromagnetic shielding film. More preferably, it is arranged so as not to contact the metal part.

  The present invention will be described more specifically with reference to the following examples. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
(Preparation of silver halide photosensitive material)
An emulsion containing 10.0 g of gelatin per 60 g of Ag in an aqueous medium and containing silver iodobromochloride grains having an average equivalent sphere diameter of 0.1 μm (I = 0.2 mol%, Br = 40 mol%) was prepared. .
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization with chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver is 1 g / m ^2. It apply | coated on the support body which consists of a polyethylene terephthalate (PET). At this time, the volume ratio of Ag / gelatin was ½.
A PET support having a thickness of 90 μm and a width of 30 cm was used. Coating was performed for 20 m with a width of 25 cm on a PET support having a width of 30 cm, and both ends were cut off by 3 cm so as to leave a central portion of the coating, thereby obtaining a roll-shaped silver halide photosensitive material.

(exposure)
For the exposure of the silver halide photosensitive material, exposure heads using the DMD (digital mirror device) described in the invention of Japanese Patent Application Laid-Open No. 2004-1244 are arranged so as to have a width of 25 cm, and a laser is formed on the photosensitive layer of the photosensitive material. The exposure head and exposure stage are curved so that light is imaged, and the photosensitive material feed mechanism and take-up mechanism are attached. The exposure was performed with a continuous exposure apparatus provided with a bend having a buffer action so as not to affect the speed. The wavelength of exposure was 400 nm, the beam shape was approximately 10 μm, and the output of the laser light source was 100 μJ.
The exposure pattern was such that a grid-like pattern with a line width of 10 μm was at an angle of 45 °, and the pitch was 24 cm wide and 10 m long at intervals of 300 μm.

(Development fixing process)
A developing solution and a fixing solution having the following formulation were prepared, and the exposed silver halide photosensitive material was subjected to development fixing processing using an automatic developing machine FG-710PTS manufactured by Fuji Photo Film Co., Ltd. The obtained sample was a mesh sample having a surface resistance of 45Ω / □.

・ Developer 1L formulation (same composition for replenisher)
Hydroquinone 22 g
Sodium sulfite 50 g
Potassium carbonate 40 g
Ethylenediamine tetraacetic acid 2 g
Potassium bromide 4 g
Polyethylene glycol 4000 1 g
Potassium hydroxide 4 g
Adjust to pH 0.2

・ 1L fixer formulation (same composition for replenisher)
Ammonium thiosulfate solution (75%) 300 ml
Ammonium sulfite monohydrate 25 g
1,3-diaminopropane tetraacetic acid 8 g
Acetic acid 5 g
Ammonia water (27%) 1 g
Adjust to pH 6.2

・ Development and fixing conditions Development 33 ° C 40 seconds Fixing 30 ° C 25 seconds Washing with running water 25 ° C 25 seconds

(Plating treatment)
Electrolytic plating in an electrolysis process to be described later was performed using a continuous electrolytic cell having a tank arrangement conceptually shown in FIG. The electrolytic bath is a bath having substantially the same function and configuration as the electrolytic plating bath 10 shown in FIG. 2, but a plurality of first-stage baths represented by a plating bath 11 filled with the copper plating solution A, Subsequently, a plurality of second-stage baths represented by the plating bath 11 filled with the copper plating solution B are configured to be a continuous configuration so as to be described later, and a plating bath is formed so that the processing described later can be performed. The plating process was performed using the electroplating apparatus which connected. Prior to the electroplating process, as a preconditioning process, a chemical process was performed using a chemical process liquid described later using a chemical process tank having the same configuration as the electroplating tank 10 in FIG. However, no voltage was applied in the chemical treatment. In addition, it attached to the electroplating apparatus so that the silver mesh surface of a film might face downward (so that a silver mesh surface might contact | connect an electric power feeding roller). The size of the plating tank 11 was 80 cm × 80 cm × 80 cm for each bath.
The power supply rollers 12a and 12b were mirror-finished stainless steel rollers (10 cmφ, length 70 cm), and the guide rollers 14 and other transport rollers were 5 cmφ and length 70 cm. In addition, by adjusting the height of the guide roller 14, a certain in-liquid processing time is ensured even if the line speed is different.

  Further, the distance (distance La shown in FIG. 2) between the lowermost part of the surface where the feeding roller 12a on the entrance side and the silver mesh surface of the film are in contact with each other was set to 9 cm. The distance (distance Lb shown in FIG. 2) between the lowermost part of the surface where the power supply roller on the outlet side is in contact with the silver mesh portion of the photosensitive material and the plating solution surface was 19 cm. Moreover, the line conveyance speed was 2.5 m / min.

  The composition plating tank of the plating treatment liquid and the rust preventive liquid in the plating treatment is as follows.

Composition of chemical treatment liquid
Glutaraldehyde 20g
1L with water

Composition of copper plating solution A
Copper sulfate pentahydrate 220g
Sulfuric acid (47%) 220mL
Hydrochloric acid (2N) 0.5mL
Polyethylene glycol 4000
(Average molecular weight 4000) 0.4 g
Janus Green B 0.05g
Bis (3-sulfopropyl) disulfide 0.05 g
Add pure water 1L
pH -0.1

Composition of copper plating solution B
200 g of copper sulfate pentahydrate
200 mL of sulfuric acid (47%)
Add pure water 1L
pH -0.1

Using these treatment liquids, a substrate sample (1) was produced under the treatment conditions shown below. Below, the processing time of a plating tank and an applied voltage are shown. Moreover, the copper plating solution A was used for the plating solution of plating 1-8, and the copper plating solution B was used for the plating solution of plating 9-16.
Moreover, the temperature of all the copper plating solutions, the washing water, the chemical treatment solution, and the rust preventive solution was 25 to 30 ° C., and the drying temperature was 50 to 70 ° C.

Chemical treatment 30 seconds
30 seconds of water washing
30 seconds of water washing
Dry 30 seconds
Plating 1 30 seconds Voltage 20V
30 seconds of water washing
Dry 30 seconds
Plating 2 30 seconds Voltage 18V
30 seconds of water washing
Dry 30 seconds
Plating 3 30 seconds Voltage 17V
30 seconds of water washing
Dry 30 seconds
Plating 4 30 seconds Voltage 12V
30 seconds of water washing
Dry 30 seconds
Plating 5 30 seconds Voltage 10V
30 seconds of water washing
Dry 30 seconds
Plating 6 30 seconds Voltage 9V
30 seconds of water washing
Dry 30 seconds
Plating 7 30 seconds Voltage 8V
30 seconds of water washing
Dry 30 seconds
Plating 8 30 seconds Voltage 7V
30 seconds of water washing
Dry 30 seconds
Plating 9 30 seconds Voltage 5V
30 seconds of water washing
Dry 30 seconds
Plating 10 30 seconds Voltage 4V
30 seconds of water washing
Dry 30 seconds
Plating 11 30 seconds Voltage 4V
30 seconds of water washing
Dry 30 seconds
Plating 12 30 seconds Voltage 3V
30 seconds of water washing
Dry 30 seconds
Plating 13 30 seconds Voltage 3V
30 seconds of water washing
Dry 30 seconds
Plating 14 30 seconds Voltage 2V
30 seconds of water washing
Dry 30 seconds
Plating 15 30 seconds Voltage 2V
30 seconds of water washing
Dry 30 seconds
Plating 16 30 seconds Voltage 1V
30 seconds of water washing
30 seconds of water washing
Dry 30 seconds

  The blackening treatment liquid described in Table 1 below was prepared.

  The blackening treatment liquid shown in Table 2 below was prepared.

  Examples 1 to 5 and Comparative Examples 1 to 4 were prepared by laminating a blackening layer on the base sample using the blackening treatment liquids in Tables 1 and 2 under the following conditions. The base sample (1) was used for all samples before the blackening layer was laminated, and the equipment used was the same as the equipment used when the base sample (1) was produced. The side closest to the fine metal wire was designated as blackening treatment 1, and the correspondence with the treatment conditions is shown in Table 3. The blank in Table 3 indicates that the blackening treatment is not performed, and Comparative Example 4 indicates that only the rust prevention treatment is performed on the base sample.

Blackening treatment 1 (side closer to fine metal wire) 45 seconds
30 seconds of water washing
Dry 30 seconds
Blackening process 2 45 seconds
30 seconds of water washing
30 seconds of water washing
Blackening 3 45 seconds
30 seconds of water washing
30 seconds of water washing
Rust prevention 45 seconds
30 seconds of water washing
Dry 1 minute 50 ° C ~ 70 ° C

The prescription of the rust preventive liquid used in the above treatment is shown.
Composition of rust prevention liquid
Benzotriazole 2.0g
20 ml of methanol
Add pure water 1L

About the obtained film sample, each metal amount was quantified as follows.
(Quantitative determination of metal in sample)
10% nitric acid is prepared, a sample immersed in 100 ml of 10% nitric acid in a certain area (7 cm × 3.5 cm) is set in an ultrasonic device for about 2 hours, and the metal in the sample is completely extracted. Thereafter, the metal concentration in the liquid was quantified using an ICP emission analyzer (manufactured by Shimadzu Corporation), and the mass ratio was calculated after obtaining the amount of metal per 1 m ^{2 of} the film sample. The results obtained are shown in Table 4. In Table 4, the denominator of each metal ratio is Ni metal, and the numerator is the other metal species coexisting in the blackening treatment liquid (in the case of the treatment liquids a, b, c, and d, Zn, the treatment liquids f and g). Sn is the case.

  The obtained samples were evaluated for visibility, color unevenness, and powder fall as follows.

(Visibility evaluation)
Each sample after the blackening treatment is bonded to a glass plate having a thickness of 2.5 mm and an external dimension of 200 mm × 200 mm with a transparent acrylic adhesive material, and placed on the front surface of the PDP. The sex was confirmed. In addition, the screens other than the visibility confirmation part are covered with black paper twice, whether the color is uncomfortable when viewing the image, whether the eyes are tired and flickering when the image is viewed for one hour And so on.
A part having no image failure in the sample before aging was selected as a test sample. However, when a failed part was inevitably included, the part was covered with black tape having a small area as much as possible. The results obtained are shown in Table 5.

(Unevenness of metal mesh film)
The center of each sample thus obtained was visually observed over a length of 1 m over a length of 1 m. The obtained results are shown in Table 5.

(Powder falling)
Using the Kimwipe S-200 (manufactured by Crecia Co., Ltd.), the blackened layer laminate surface of each sample thus obtained was subjected to a 5-reciprocal rubbing test with a load of 20 g. The sample after the test was observed with an optical microscope, and the evaluation was evaluated as x when peeling was observed on the blackened layer and falling around the fine line in a powdery state, and ○ when peeling was not seen. The results are shown in Table 5.

As can be seen from Table 5, it can be seen that the sample of the present invention satisfies the required performance of visibility, uneven coloring, and powder falling off.
In addition, the sample of the present invention described above had a small change in color after wet heat aging and was excellent in adhesion. Further, the surface resistance is 0.4Ω / □ or less, the total light transmittance is 80% or more, and the haze is 5% or less, and it can be suitably used as an electromagnetic wave shielding film for PDP.

It is a figure for demonstrating the electroplating process in this invention. It is a schematic diagram which shows an example of the electroplating tank suitably used for the plating method of this invention.

Explanation of symbols

a to f Electrolysis tank 1 Film 10 Electroplating tank 11 Plating tank 12a, 12b Feed roller 13 Anode plate 14 Guide roller 15 Copper plating solution 16 Film 17 Liquid cutting roller

Claims (8)

In a translucent conductive material having a conductive metal layer formed by patterning a metal part and a visible light transmissive part on a transparent substrate, at least two different alloy compositions are formed on the metal thin wire constituting the metal part. The blackening layer of the layer is laminated , the laminated blackening layer has two or more metal elements including nickel and at least one metal selected from zinc and tin, and the mass of the nickel / other metal A light-transmitting conductive material having a ratio of 0.1 to 50, wherein the mass ratio is gradually decreased from a layer closest to the metal fine wire of the metal portion toward a layer farther away. The blackening layer is a two-layer alloy composed of nickel and zinc, and the nickel / zinc mass ratio of the blackening layer on the side close to the fine metal wire is 3 to 15, and the nickel / zinc mass ratio of the blackening layer on the surface layer side The translucent conductive material according to claim 1 , wherein is 0.1-3. And said black layer is an alloy of two layers of nickel and tin, nickel / tin weight ratio of the blackened layer on the side closer to the thin metal wires 1-2, nickel / tin weight ratio of the surface layer side of the blackened layer The translucent conductive material according to claim 1, wherein is 0.1 to 1 . The translucent conductive material according to any one of claims 1 to 3 , wherein the metal portion is formed from a pattern including a mesh-like thin line having a line width of 5 µm to 50 µm. The translucent conductive material according to any one of claims 1 to 4 , wherein the conductive metal layer contains gelatin. ToruHikarishirube conductive material according to any one of claims 1 to 5, characterized in that a conductive metal portion formed by electrolytic plating in ToruHikarishirube conductive material patterned on developed silver. The translucent conductive material according to any one of claims 1 to 6 , wherein the blackening layer is formed by multi-stage electrolytic plating. Light-transmitting electromagnetic wave-shielding film comprising a ToruHikarishirube conductive material according to any one of claims 1-6.

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