JP2007207910A - Translucent electromagnetic wave shielding film, optical filter and plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost translucent electromagnetic wave shielding film which can be manufactured with the less number of processes, has sufficient conductivity, i. e. electromagnetic wave shielding performance and sufficient surface hardness, is excellent in durability such as heat resistance and humidity-heat resistance, and has small light diffusion and high light transmittivity, and to provide an optical filter and a plasma display panel which employ this film. <P>SOLUTION: In the translucent electromagnetic wave shielding film, minute wires like a mesh having a wire width of 1 μm-30 μm containing silver as a main component are formed on a transparent substrate. In this film, the mesh-like minute wires are acquired by firstly forming a mesh pattern on the transparent substrate by printing, and then, applying electrolytic plating to the mesh pattern, and the mesh-like minute wires continue ≥3 m in a longitudinal direction of the translucent electromagnetic wave shielding film. The optical filer and the plasma display panel each employs this film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a display such as a CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, ELP (electroluminescence panel (EL)), FED (field emission display), a microwave oven, an electronic device, The present invention relates to a translucent electromagnetic wave shielding film that shields electromagnetic waves generated from a printed wiring board and the like and has translucency, an optical filter including the translucent electromagnetic wave shielding film, and a plasma display panel.

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. 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.

  Although it is necessary to shield the electromagnetic wave as a countermeasure against the EMI, 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., since the operator needs to recognize characters displayed on the screen, transparency in the display is required. For this reason, in any of the above methods, the front surface of the display often becomes opaque, which is inappropriate as an electromagnetic wave shielding method.

Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. In a translucent electromagnetic wave shielding film for CRT, the surface resistance value is required to be about 300Ω / sq or less, whereas for PDP The translucent electromagnetic wave shielding film requires 2.5Ω / sq or less, and in a plasma plasma for consumer use using a PDP, there is a high need for 1.5Ω / sq or less, and more desirably 0.1Ω / sq. An extremely high conductivity of sq or less is required.
Further, the required level of transparency is about 70% or more for CRT and 80% or more for PDP, and further higher transparency is desired.

  In order to solve the above problems, as shown below, various materials and methods have been proposed so far that achieve both electromagnetic shielding properties and light transmittance using a metal mesh having an opening, A typical example is an etched metal mesh using a photolithography method. Etching-processed metal meshes using conventional photolithography methods can be finely processed, so it is possible to create metal meshes with high aperture ratio (high transmittance) and shield strong electromagnetic wave emission. Have. On the other hand, the manufacturing process is complicated and has a problem of high cost, and improvement is demanded.

As a method for producing a metal mesh at a low cost, a method for obtaining a metal mesh by printing a paste or ink containing metal particles in a lattice pattern has been proposed.
For example, Patent Document 1 discloses a method of manufacturing an electromagnetic wave shielding material by printing a conductive fine particle dispersion such as silver by an ink jet method, heating and baking.
Patent Document 2 discloses a method for producing an electromagnetic wave shielding film by printing a paste having a silver compound and then heating to promote reduction / decomposition into a metal and promoting fusion between metals. It is disclosed.

JP 2003-318593 A Japanese Patent Application Laid-Open No. 2004-111988

The metal mesh obtained by using the conventional printing method as described above can be manufactured with a smaller number of steps and can reduce the manufacturing cost as compared with the manufacturing process of the etched metal mesh using photolithography. On the other hand, it had the following problems.
The first point is that the conductivity of the metal mesh tends to be smaller than when the metal foil is etched, which is disadvantageous in terms of electromagnetic shielding performance.
Secondly, there was a problem that the metal mesh and the support were not sufficiently adhered, and the resistance to physical and mechanical actions such as scratching, that is, the surface hardness was weak.
The third point is that the durability required for the electromagnetic wave shielding film used for the display is not sufficient, and improvement has been desired.
As a result of investigations by the present inventors, it was found that the metal phase of the metal mesh is not a complete continuous phase but is likely to be an aggregate phase of metal fine particles having a large surface area in order to print a fine particle dispersion of a metal or metal compound. . This is considered to be part of the above problem.

Further, in the conventional method of forming a metal mesh etched using photolithography, a mesh pattern can be created only in a certain area, and a continuous mesh that is continuous for several tens of meters or more in the longitudinal direction of the roll, Could not be manufactured. The reason for this is that, in the formation of an etching-processed metal mesh using photolithography, the exposure method is repeatedly exposed once in a single wafer exposure photomask size unit, and continuously exposed over a long roll film. Because it is something that cannot be done.
For this reason, for example, in the case of a PDP application, a manufacturing method is used in which the electromagnetic shielding film is aligned with an optical filter material based on the created electromagnetic shielding film mesh pattern and PDP module or front plate or glass. I came. In this method, the shielding material is lost, and in order to improve productivity, even if a roll-shaped shielding material is used, it takes time to align each mesh pattern and the panel, thereby reducing the production speed. I couldn't raise it enough.

Furthermore, in the electromagnetic wave shielding film as described above, near infrared cut performance is an important required characteristic for the purpose of preventing malfunction of the remote control. In particular, with the recent increase in the brightness of PDPs, the amount of near infrared rays generated has increased, so that even higher near infrared ray cutting performance is required.
Giving this near-infrared cut function is considered to be obtained by laminating the functional layer with an electromagnetic wave shielding film, etc., but the electromagnetic wave shielding film is intermittent as described above and has a large amount of loss. As long as an optical filter is produced while producing a film, a film having a near-infrared cut function also has a drawback of being used only intermittently.
In addition, in PDP applications, an antireflection function is indispensable in addition to the above electromagnetic wave shielding ability and near infrared ray cutting ability. Since this anti-reflection film or functional film is a roll-like film as well as a film having a near-infrared cut function, when the electromagnetic wave shielding film has a discontinuous mesh pattern and is bonded to the anti-reflection film In addition, there is a problem that a loss portion where the antireflection film is not used is generated.

  The present invention has been made in view of such circumstances, and the object of the present invention is low-cost and sufficient that can be manufactured with a smaller number of steps as compared to a manufacturing process of an etched metal mesh using photolithography. It is to provide a translucent electromagnetic wave shielding film having electrical conductivity, that is, electromagnetic wave shielding performance, and has sufficient surface hardness, excellent adhesion, excellent durability such as heat resistance, moist heat resistance, and light scattering. The present invention provides a translucent electromagnetic shielding film, an optical filter using the same, and a plasma display panel.

The present invention is as follows.
(1)
A translucent electromagnetic wave shielding film in which a fine mesh wire having a line width of 1 μm to 30 μm mainly composed of silver is formed on a transparent substrate, wherein the fine mesh wire is first formed on the transparent substrate After the mesh pattern is formed by printing, the mesh pattern is obtained by further electrolytic plating, and the mesh-like fine line is continuously 3 m or more in the longitudinal direction of the translucent electromagnetic shielding film. A translucent electromagnetic wave shielding film characterized by comprising:
However, in the present invention, “having silver as a main component” means that silver is contained in an amount of 60% by mass or more with respect to the metal constituting the mesh-like fine wire. “Translucent” means that the spectral transmittance is 50% or more over the entire wavelength range of 380 to 780 nm.
(2)
The surface resistance of the transparent substrate after forming the mesh pattern by the printing is 1Ω / □ to 100Ω / □, and then the electrolytic pattern is applied to the mesh pattern (1 ).
(3)
The translucent electromagnetic wave shielding film according to (1) or (2), wherein after the mesh pattern is formed by the printing, the mesh pattern is calendered.
(4)
The translucent electromagnetic wave shielding film according to (3), wherein the calendar treatment is performed at a linear pressure of 1960 N / cm (200 kgf / cm) or more.
(5)
The translucent electromagnetic wave shielding film according to any one of (1) to (4), wherein the mesh-like fine wire contains a rust inhibitor.
(6)
The translucent electromagnetic wave shielding film according to any one of (1) to (5), wherein an easy adhesion layer is provided between the transparent base material and the mesh-like fine wire.
(7)
(6) The adhesive layer is provided on the easy-adhesion layer so that the peel strength of adhesion through the easy-adhesion layer between the transparent base material and the glass substrate is 20 N / m or more. Translucent electromagnetic shielding film.
(8)
The translucent electromagnetic wave shielding film according to (7), wherein the peel strength after leaving for 75 hours at 60 ° C. and a humidity of 90% or more is 20 N / m or more.
(9)
The translucent electromagnetic wave shield according to any one of (1) to (8), wherein the electrolytic plating is a plating treatment for plating at least one selected from copper, nickel, zinc, tin, and cobalt. film.
(10)
An optical filter comprising the translucent electromagnetic wave shielding film according to any one of (1) to (9).
(11)
A plasma display panel comprising the translucent electromagnetic wave shielding film according to any one of (1) to (9).

  According to the present invention, compared to a manufacturing process of an etched metal mesh using photolithography, it can be manufactured with a small number of steps and has sufficient conductivity, that is, electromagnetic wave shielding performance, and surface hardness. Translucent electromagnetic wave shielding film with sufficient light resistance, excellent adhesion, excellent durability such as heat resistance and moist heat resistance, small light scattering and high light transmittance, optical filter and plasma display panel using the same Can be provided.

The present invention is described in further detail below. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.
Further, in this specification, “mesh” in “continuous mesh pattern” or the like refers to a mesh pattern composed of a plurality of fine lines or a mesh composed of a plurality of thin lines according to an example in the art.
Furthermore, the meaning of “continuous” refers to a long film such as a roll, and means that the same pattern is continuous in the length direction of the long film.
In addition, since the “electromagnetic wave shielding film” is carried on a film-like transparent substrate, it is referred to as “electromagnetic wave shielding film” or simply “film” as long as there is no confusion with other components (component films) to be laminated. Sometimes.

[Transparent substrate]
Examples of the transparent substrate used in the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene and EVA; polyvinyl chloride, poly Vinyl resins such as vinylidene chloride; others such as polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), etc. The transparent plastic substrate can be used.
In the present invention, the transparent substrate is preferably a polyethylene terephthalate film from the viewpoints of transparency, heat resistance, ease of handling, and cost. The thickness of the transparent substrate is preferably 200 μm or less from the viewpoints of handleability and visible light transmittance. More preferably, they are 20 micrometers or more and 180 micrometers or less, More preferably, they are 50 micrometers or more and 120 micrometers or less.

Since the electromagnetic shielding film for a display panel requires transparency, it is desirable that the substrate has high transparency. In this case, the total visible light transmittance of the transparent substrate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not prevented as said transparent base material can also be used.
Although the transparent base material in this invention can also be used by a single layer, it can also be used as a multilayer film which combined two or more layers.

  In the present invention, a glass plate can also be used as the transparent substrate. Although the kind of glass plate is not specifically limited, When using as a use of the electromagnetic wave shielding film for a display, it is preferable to use the tempered glass which provided the reinforced layer on the surface. There is a high possibility that tempered glass can prevent damage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

[Mesh-like fine lines]
Next, the mesh-like fine wire (conductive metal part) mainly containing silver in the present invention will be described.
As a printing method, a known printing method such as gravure printing, offset printing, letterpress printing, screen printing, flexographic printing, inkjet printing, or the like can be used. Of these, screen printing, offset printing, and intaglio printing are preferable, and screen printing and gravure printing are particularly preferable.
A surface treatment may be performed on the transparent substrate, or an anchor coat layer may be provided. Effective surface treatment methods include primer coating, plasma treatment, corona discharge treatment, and the like. The critical surface tension of the transparent substrate after the treatment is preferably 3.5 × 10 ⁻⁴ N / cm or more by these treatments, and more preferably 4.0 × 10 ⁻⁴ N / cm or more.

  In the present invention, the conductive metal portion is preferably inclined at 30 ° to 60 ° with respect to the longitudinal direction of the translucent electromagnetic shielding film. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °.

The paste or ink used for printing preferably contains a metal or a metal compound for obtaining a mesh pattern (printing pattern) by printing, and also contains a solvent, a binder, a dispersing agent and the like for dispersing them.
Examples of the metal include fine particles such as silver, copper, nickel, palladium, gold, platinum, and tin. In the present invention, the printing pattern is mainly composed of silver, and silver alone or two or more kinds containing silver are included. You may mix and use the said metal. However, the printing pattern which has silver as a main component refers to the printing pattern whose mass% of silver with respect to the metal which comprises this pattern is 60% or more. In this invention, when using 2 or more types of metals, it is also preferable to coat | cover with one metal.
In the present invention, a metal compound can also be used. The metal compound is a metal oxide or an organometallic compound, and a compound that can easily reduce or decompose by applying energy from the outside and can impart conductivity is preferable. As the metal oxide, gold oxide, silver oxide, or the like can be used. In particular, silver oxide is preferable because it has self-reducing properties. As the organometallic compound, silver acetate, silver citrate and the like having a relatively small molecular weight are preferable. In the case where the paste contains a metal, for example, it is preferably made from a nano-order size (5 to 60 nm) metal, a dispersant, and a solvent. In addition, when the paste contains a metal oxide, it is preferably made from a nano-order size metal oxide, a reducing agent necessary for the reduction of the metal oxide, and a solvent. It is preferable to prepare from an organometallic compound having a low temperature and a solvent. Above all, when a paste using a combination of nano-order size metal oxide and organometallic compound is used, not only can fine lines be printed, but also external energy can be applied by appropriately selecting the structure of the reducing agent and organometallic compound. When imparting electrical conductivity, it is possible to promote reductive decomposition from metal oxide to metal under conditions that do not damage the flexible film, and to promote fusion between metals. Further, the resistance value can be further reduced. In addition, when a metal oxide can be reduced without adding a reducing agent, for example, when it can be self-reduced by heating, it is not particularly necessary to add a reducing agent. As the solvent, which will be described later in detail, it can be appropriately used depending on the printing method and paste viscosity adjusting method to be used, and a high boiling point solvent such as carbitol and propylene glycol can be used. The viscosity of the paste can be appropriately set according to the printing method and the solvent to be used, but is preferably 5 mPa · s or more and 20000 mPa · s or less.

  Examples of the binder contained in the paste and ink used in the present invention include the following resins such as polyester resin, polyvinyl butyral resin, ethyl cellulose resin, (meth) acrylic resin, polyethylene resin, polystyrene resin, polyamide resin and the like. Any of thermosetting resins such as plastic resin; polyester-melamine resin, melamine resin, epoxy-melamine resin, phenol resin, epoxy resin, amino resin, polyimide resin, and (meth) acrylic resin can be used. Two or more kinds of these resins may be copolymerized as required, or two or more kinds may be blended and used.

  Specific examples of usable solvents include hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, seryl alcohol, cyclohexanol, terpineol and other alcohols; ethylene glycol monobutyl ether (Butyl cellosolve), ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and other alkyl ethers. It may be selected as appropriate in consideration.

  When higher alcohol is used as the solvent, the drying and fluidity of the ink may decrease, so butyl carbitol, butyl cellosolve, ethyl carbitol, butyl cellosolve acetate, butyl carbitol acetate, etc. have better drying properties than these May be used in combination. The amount of the solvent used is determined by the viscosity of the ink or paste, but is usually 100 to 500 parts by weight, preferably 100 to 300 parts by weight with respect to 100 parts by weight of the binder in consideration of the amount of the metal powder added. It is good to be.

Metal, as a binder, and a solvent component ratio (mass ratio), with respect to for example, metal 1, a binder ¹⁰ -5 to 10 ^2, solvent 10 ^5, preferably to a metal 1, a binder ¹⁰ -3 to 10, solvent 10 to 10 is ^three.
The conductive metal part after printing is preferably fired at a high temperature. Thereby, the organic component is removed and the metal fine particles adhere to each other, and the surface resistance value is lowered. The firing temperature is, for example, 50 to 1000 ° C., preferably 70 to 600 ° C., and the firing time is, for example, 3 to 600 minutes, preferably 10 to 300 minutes.

  Since the translucent electromagnetic wave shielding film in the present invention has a conductive metal part, good conductivity can be obtained. For this reason, the surface resistance value of the translucent electromagnetic wave shielding film of the present invention is preferably 10Ω / sq or less, more preferably 2.5Ω / sq or less, and 1.5Ω / sq or less. Is more preferable, and most preferably 0.1Ω / sq or less.

In the conductive metal portion of the present invention, the conductive metal is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or the like, (positive) hexagon, (positive) It is preferably arranged so as to constitute a geometric figure combining octagons and the like, and more preferably a mesh shape composed of these geometric figures.
In the present invention, it is most preferable to have a grid-like mesh form composed of squares.

  The line width of the conductive metal part is 1 to 30 μm, preferably 20 μm or less, and the line interval is preferably 100 μm or more. The conductive metal portion may have a portion whose line width is wider than 30 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is more preferably less than 15 μm.

  The thickness of the conductive metal portion is preferable for the display panel because the viewing angle of the display is increased as the thickness is reduced. It is preferably less than 9 μm, more preferably from 0.1 μm to less than 5 μm, and even more preferably from 0.1 μm to less than 3 μm. The conductive metal portion may be a single layer or a multilayer structure of two or more layers.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. Further, the “aperture ratio” is a ratio of a portion having no fine line 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 approximately 90%. In addition, although there is no restriction | limiting of an upper limit in particular regarding the aperture ratio of the electroconductive metal part in this invention, As said aperture ratio, it is preferable that it is 98% or less from the relationship between a surface resistance value and a line | wire width value.

A calendar process preferably used in the present invention, that is, a process using a calendar roll will be described.
In this invention, it is preferable that the mesh pattern (printing pattern) formed by printing on the transparent base material is processed with a calender roll. Thereby, it is possible to improve the electroconductivity of the printing pattern part which has silver as a main component, and it is possible to improve electromagnetic wave shielding performance.
A calendar roll usually consists of one or more pairs of rolls. As a roll used for the calendar process, a plastic roll or a metal roll such as epoxy, polyimide, polyamide, polyimide amide or the like is used. It is particularly preferable to treat with metal rolls. The linear pressure is preferably 1960 N / cm (200 kgf / cm) or more, more preferably 2940 N / cm (300 kgf / cm) or more.
The temperature of the calender roll treatment is preferably 10 ° C to 100 ° C, more preferably 10 ° C to 50 ° C.
This calendar process can continuously process a roll-like long film.

The mesh-like fine wire in the present invention needs to be continuous for 3 m or more in the longitudinal direction of the translucent electromagnetic wave shielding film. However, as the continuous length of the fine wire increases, for example, the loss in producing an optical filter material decreases. Since it can do, it can be said that it is a more preferable aspect. On the other hand, if the continuous length is too long, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness. It is preferable that it is 2000 m or less. Preferably they are 100 m or more and 1000 m or less, More preferably, they are 200 m or more and 800 m or less, Most preferably, they are 300 m or more and 500 m or less.
For the same reason, the thickness of the transparent substrate is preferably 200 μm or less, more preferably 20 μm or more and 180 μm or less, and most preferably 50 μm or more and 120 μm or less.

Next, the electroplating applied to the present invention will be described. The electrolytic plating is preferably a step of plating at least one selected from copper, nickel, zinc, tin and cobalt. Hereinafter, description will be made by taking electrolytic plating as an example.
FIG. 1 shows an example of an electrolytic plating tank suitably used for the plating treatment according to the present invention. The electrolytic plating tank 10 shown in FIG. 1 is capable of continuously plating a long film 16. The arrow indicates the conveyance direction of the film 16. The electrolytic plating tank 10 includes a plating bath 11 that stores a plating solution 15. 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 disposed. A liquid draining roller 17 is rotatably disposed above the plating bath 11 and below the outlet-side power feeding roller 12b. Between the liquid draining roller 17 and the outlet-side power feeding roller 12b. Is provided with a water spray (not shown) for removing the plating solution from the film.
The anode plate 13 is connected to a plus terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 12a and 12b are connected to a minus terminal of the power supply device (not shown). .

In the above-described electrolytic plating tank 10, for example, when the size of the electrolytic plating tank is 10 cm × 10 cm × 10 cm to 100 cm × 200 cm × 300 cm, the lowermost part of the surface where the feeding roller 12 a 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 cm to 15 cm, more preferably 1 cm to 10 cm, and even more preferably 1 cm 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 is in contact with the film 16 and the plating solution surface is 0.5 cm to 15 cm.

Next, a method for reinforcing the conductivity by forming a copper plating layer on the mesh-like silver fine wire pattern of the film using the plating apparatus provided with the electrolytic plating tank 10 will be described.
First, the plating solution 15 is stored in the plating bath 11. As the plating solution, in the case of copper plating, a copper sulfate pentahydrate containing 30 g / L to 300 g / L and sulfuric acid containing 30 g / L to 300 g / L can be used. In the case of nickel plating, nickel sulfate, nickel hydrochloride or the like can be used, and in the case of iron silver plating, one containing silver cyanide or the like can be used. Moreover, you may add additives, such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.

The film 16 is set in a state where it is wound around a supply reel (not shown), and the film 16 is transported so that the surface of the film 16 on which the plating should be formed contacts the power supply rollers 12a and 12b. Wrap it around (not shown).
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 plating bath 11 and immersed in the plating solution 15 to form a copper plating. When passing between the liquid draining rollers 17, the plating solution 15 adhered to the film 16 is wiped off and collected in the plating bath 11. This is repeated in a plurality of electrolytic plating tanks, finally washed with water, and then wound up on a take-up reel (not shown).
The conveyance speed of the film 16 is set in the range of 1 m / min to 30 m / min. The conveyance speed of the film 16 is preferably in the range of 1 m / min to 10 m / min, and more preferably in the range of 2 m / min to 5 m / min.

The number of electrolytic plating tanks is not particularly limited, but is continuous, for example, 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.
The applied voltage is preferably in the range of 1V to 100V, more preferably in the range of 2V 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. Further, the current amount on the inlet side of 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).

  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.

  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 wave shielding film of 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 plated conductive metal part is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and further preferably 0.1 μm or more and less than 3 μm. preferable.

In the plating treatment of the present invention, if the film has a surface resistance of 1Ω / □ to 1000Ω / □ immediately before the electrolytic plating treatment, an electroless plating treatment may be performed before that. Electrolytic plating without electroless plating is preferable in terms of productivity and cost because the number of steps is small.
When performing electroless plating, a known electroless plating technique can be used, for example, an electroless plating technique used in a printed wiring board or the like can be used. Preferably there is.
Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agent, formalin, glyoxylic acid, copper ligand, EDTA, triethanolamine, etc., bath stabilization and plating Examples of the additive for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine.

  In the present invention, as long as the surface resistance of the transparent substrate after forming the mesh pattern by printing has a film surface of 1Ω / □ to 1000Ω / □, electroplating can be applied to any of them. . A preferable surface resistance is 1Ω / □ to 500Ω / □, and a more preferable range is 1Ω / □ to 100Ω / □.

Next, the rust inhibitor used in the present invention will be described.
As the rust preventive agent used in the present invention, a nitrogen-containing organic heterocyclic compound or an organic mercapto compound is preferably used.
Preferable examples of the nitrogen-containing organic heterocyclic compound include the following.
That is, imidazole, benzimidazole, benzoindazole, benzotriazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine, etc., these include alkyl groups, carboxyl groups, sulfo groups, etc. May have the following substituents.
Examples of the organic mercapto compound include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.

Preferably, it is an organic mercapto compound represented by the following general formula (2).
General formula (2)
Z-SM
[In General Formula (2), Z is an alkyl group, an aromatic group, or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² is a hydrogen atom or an alkali metal atom) Or an ammonium group), at least one group selected from the group consisting of an amino group and an ammonio group, or a group substituted by a substituent having at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]

Also preferred are organic mercapto compounds represented by the following general formulas (1), (3), and (5).
General formula (1)

[In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group,, ^{R 0} represents a substituent. L ¹ , L ² and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring through any of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Provided that at least one of ^{L 1,} L 2, ^{L 3} and ^{R 0} is representative of the -SM group (M represents an alkali metal atom, a hydrogen atom or an ammonium group). ]

General formula (3)

[In General Formula (3), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group. However, R ₂₁ and R ₂₂ are not simultaneously a hydrogen atom, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group, and R ₂₅ represents a hydroxyl group, an amino group, an alkyl group or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group, an acyl group, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group, an alkali metal atom, an aryl group or an aralkyl group. m represents 0, 1 or 2. ]

General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and Ma are a hydrogen atom, an alkali metal atom or ammonium, respectively. Represents a group. ]

  The compound represented by the general formula (2) will be described.

  In the general formula (2), the alkyl group represented by Z is preferably one having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, the above-mentioned You may have a substituent other than a substituent. The aromatic group represented by Z is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above-described substituents. The heterocyclic group represented by Z is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and has 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur in one ring. It is a 5- or 6-membered ring and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (2), a compound in which Z is a heterocyclic group having two or more nitrogen atoms is preferable.

  A preferable compound represented by the general formula (2) is represented by the following formula (2-a).

In the general formula (2-a), Z forms an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.) A group having at least one —SM group or thione group, and having a hydroxyl group, —COOM group, —SO ₃ M group, substituted or unsubstituted amino group, substituted or unsubstituted Having at least one substituent selected from the group consisting of substituted ammonio groups. In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom, —SM group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), a hydroxyl group, -COOM group, -SO 3 _M group, (including those having a substituent) alkenyl group (including those having a substituent) amino group, (including those having a substituent) carbamoyl group, a phenyl group (substituted Including a group having a group), and R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered ring or a 6-membered ring, preferably a nitrogen-containing heterocycle. M is synonymous with M defined in the general formula (2). Z is preferably a group that forms a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the -SM group or thione group, and the substituent includes a halogen atom, Lower alkyl groups (including those having substituents, preferably those having 5 or less carbon atoms such as methyl and ethyl groups), lower alkoxy groups (including those having substituents; carbons such as methoxy, ethoxy and butoxy) And a lower alkenyl group (including those having a substituent. Preferred are those having 5 or less carbon atoms), a carbamoyl group, a phenyl group, and the like. Furthermore, the compounds represented by the following formulas A to F in the general formula (2-a) are particularly preferable.

In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently a hydrogen atom, —SM group, halogen atom, lower alkyl group (including those having a substituent. Carbon number such as methyl group, ethyl group, etc. 5 or less are preferred), a lower alkoxy group (including those having a substituent, preferably those having 5 or less carbon atoms), a hydroxy group, —COOM ² , —SO ₃ M ⁵ group, a lower alkenyl group ( Including those having a substituent, preferably those having 5 or less carbon atoms), an amino group, a carbamoyl group, and a phenyl group, at least one of which is an -SM group. M, M ² and M ⁵ each represent a hydrogen atom, an alkali metal atom or an ammonium group. In particular, hydroxy groups as substituents other than _{^{-SM, -COOM 2, -SO 3 M}} 5 group, it preferably has a water-soluble group such as an amino group.

The amino group represented by R ²¹ , R ²² , R ²³ , R ²⁴ represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group. The ammonium group represented by M, M ² and M ⁵ is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

  Although the specific example of a compound represented by General formula (2) below is shown, it is not limited to these.

  The compounds represented by the general formulas (1), (3), and (5) will be described.

The compound represented by the general formula (1) will be described in detail. In the general formula (1), -D = and -E = each independently -CH = group, -C ^(R 0) = represents a group or -N = group, wherein the ^{R 0} is a substituent. L ^{1, L 2,} L ³ each independently represent a hydrogen atom, he represents a halogen atom or a carbon atom, a nitrogen atom, an oxygen atom, an optional substituent attached to the ring either sulfur or phosphorus atom, L ¹ ~L ³ may be the same or different. However, at least one of L ¹ , L ² , L ³ and R ¹ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group). ]

Specific examples of the optional substituent represented by L ¹ , L ² , and L ³ and the substituent represented by R ⁰ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing quaternized nitrogen atom (for example, pyridinio group), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group unit Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group , Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino Group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, ( (Alkyl, aryl or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, And a group containing a phosphoric acid amide or phosphoric acid ester structure. These substituents may be further substituted with these substituents.

More preferably, the arbitrary substituents represented by L ¹ , L ² and L ³ and the substituent represented by R ⁰ are a substituent having ⁰ to 15 carbon atoms, such as a chlorine atom, an alkyl group, an aryl group, a complex A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a cyano group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocyclic ring) amino group, a hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio Group, a sulfo group or a salt thereof, and a sulfamoyl group, and more preferably an alkyl group, an aryl group, a complex Group, alkoxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, hydroxyamino group, N-substituted saturated or unsaturated A saturated nitrogen-containing heterocyclic group, acylamino group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, sulfo group or a salt thereof; Most preferred are amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group, mercapto group, carboxy group or salt thereof, sulfo group or salt thereof. In the general formula (1), L ¹ , L ² , L ³ and R ⁰ may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In General Formula (1), at least one of L ¹ , L ² , L ³ , and R ¹ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group). Here specifically the alkali metal atom is Na, K, Li, Mg, Ca, etc., it -S ^- present as a counter cation. M is preferably a hydrogen atom, an ammonium group, Na ⁺ , or K ⁺ , and particularly preferably a hydrogen atom. Among the compounds represented by the general formula (1), compounds represented by the following general formula (1-A) and general formula (1-B) are preferable.

Next, the general formula (1-A) will be described in detail. R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by the general formula (1) And L ¹ , L ² , and L ³ have the same meanings, and preferred ranges thereof are also the same. However, R ¹ and R ³ do not represent a hydroxy group. R ^{1 to} R ⁴ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. R ¹ and R ² may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In general formula (1-A), at least one of R ^{1 to} R ⁴ is an —SM group, and more preferably at least two of R ^{1 to} R ⁴ are —SM groups. When at least two of R ^{1 to} R ⁴ are —SM groups, preferably R ⁴ and R ¹ , or R ⁴ and R ³ are —SM groups.

  In the present invention, among the compounds represented by the general formula (1-A), compounds represented by the following general formulas (1-A-1) to (1-A-3) are particularly preferable.

In the general formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In the general formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ²⁰ represents a hydrogen atom or an arbitrary substituent. In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. However, R ¹⁰ and Y ¹ do not represent a hydroxy group.

Next, the compounds represented by the general formulas (1-A-1) to (1-A-3) will be described in detail.
In General Formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent. Here, the arbitrary substituents are the same as those described for R ^{1 to} R ^{4 in} the general formula (1-A). R ¹⁰ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamido group, alkylthio group, arylthio group, alkylamino group, arylamino group and the like can be mentioned. In general formula (1-A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid group or a carboxylic acid group and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group that can be partially or completely dissociated by an alkaline developer. Specifically, sulfo group (or salt thereof), carboxy group (or salt thereof), hydroxy group, mercapto group, amino group, ammonio group, sulfonamido group, acylsulfamoyl group, sulfonylsulfamoyl group, active methine Represents a group or a substituent containing these groups. In the present invention, the active methine group means a methyl group substituted with two electron-withdrawing groups, specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy. Examples include groups such as carbonylmethyl. The substituent represented by X in the general formula (1-A-1) is the above-described water-soluble group or a substituent substituted with the above-mentioned water-soluble group, and the substituent has 0 carbon atoms. ˜15 substituents, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkyl, aryl or heterocyclic) amino group, an acylamino group, a sulfonamide group, Examples include ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocyclic) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like. 10 alkyl groups (especially methyl groups substituted with amino groups), aryl groups, aryloxy groups, amino groups, (alkyl, aryl, or Ring) amino group, an (alkyl, aryl or heterocyclic) group such as thio group.

  Among the compounds represented by the general formula (1-A-1), a compound represented by the following general formula (1-A-1-a) is more preferable.

Wherein ^{R 11} has the same meaning as ^{R 10} in formula (1-A-1), and the preferred range is also the same. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However, at least one of R ¹² and R ¹³ has at least one water-soluble group. Here, the water-soluble group is a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamide group, an acylsulfamoyl group, or a sulfonylsulfamoyl group. Represents a group, an active methine group, or a substituent containing these groups, and preferred examples include a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, an amino group, and the like. R ¹² and R ¹³ are preferably an alkyl group or an aryl group, and when R ¹² and R ¹³ are an alkyl group, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, As the substituent, a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ are an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and the substituent is a water-soluble group, particularly a sulfo group (or a salt thereof). , A carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ represent an alkyl group or an aryl group, they may be bonded to each other to form a cyclic structure. A saturated heterocyclic ring may be formed by a cyclic structure.

In General Formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and has the same meaning as X in General Formula (1-A-1). In the general formula (1-A-2), the water-soluble group represented by Y ¹ or the substituent substituted with the water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, That is, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. Y ¹ is more preferably an active methine group or an amino group (alkyl, aryl, or heterocyclic) substituted with a water-soluble group, wherein the water-soluble group includes a hydroxy group, a carboxy group or a salt thereof, sulfo A group or a salt thereof is particularly preferred. Y ¹ is particularly preferably an (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ⁰¹ ) It is represented by (R ⁰² ) group. R ⁰¹ and R ⁰² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A), respectively, and preferred ranges thereof are also the same.

In the general formula (1-A-2), R ²⁰ represents a hydrogen atom or an arbitrary substituent, and here, the arbitrary substituent is the one described for R ^{1 to} R ^{4 in} the general formula (1-A). The same thing is mentioned. R ²⁰ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a hydroxylamino group and the like can be mentioned. R ²⁰ is most preferably a hydrogen atom.

In General Formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. Y ² and R ³⁰ in formula (1-A-3) are the same groups as Y ¹ in formula (1-A-2) and R ^{20 in} formula (1-A-2), respectively. The range is also the same.

Next, the general formula (1-B) will be described in detail. ^R 5 to R ⁷ in the formula (1-B) has the same meaning as ^R 1 to R ⁴ of formula (1-A) independently, the preferred range thereof is also the same. Of the compounds represented by the general formula (1-B), the compound represented by the general formula (1-B-1) is particularly preferable.
Formula (1-B-1)

In the general formula (1-B-1), R ⁵⁰ has the same meaning as R ^{5 to} R ^{7 in the} general formula (1-B), and more preferably the general formulas (1-A-1) to (1-A- 3) a water-soluble group having the same meaning as X, Y ¹ , and Y ² or a group substituted with a water-soluble group. Furthermore, among the compounds of general formula (1-B-1), the compound represented by general formula (1-B-1-a) is most preferable.
General formula (1-B-1-a)

In the general formula (1-B-1-a), R ⁵¹ and R ⁵² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A-1-a), and preferred ranges thereof are also the same. .

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is not limited to these.

In the general formula (3), the alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ preferably has 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc. The alkyl group represented by R ₂₆ and R ₂₇ preferably has 1 to 5 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and the like, Preferably it has 18 or less carbon atoms, and examples thereof include an acetyl group and a benzoyl group. The alkyl group represented by M ₂₂ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and the aryl group includes a phenyl group, a naphthyl group, and the like as an aralkyl group. Preferably has 15 or less carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

  Although various synthetic methods are known for the compound represented by the general formula (3), for example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. Alkaline and acetic anhydride are added alternately.

  Next, although the specific example of a compound represented by General formula (3) is shown, this invention is not limited only to these.

The lower alkyl group represented by X _{40 in} the general formula (5) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an isopropyl group. Although the example of a specific compound represented by General formula (5) is shown, it is not limited to these.

In the present invention, these rust inhibitors can be used alone or in combination of two or more.
The rust preventive agent used in the present invention is applied to the conductive metal part by, for example, immersing a transparent base material in which the conductive metal part is formed in the aqueous solution after making the aqueous solution. The rust prevention treatment is preferably performed on the conductive metal part after the firing treatment. The aqueous rust inhibitor solution used at this time is, for example, a compound represented by the general formula (1), (2), (3), or (5) in a liter of 10 ⁻⁶ to 10 ^−1. It is preferable to contain it as a concentration of mol, preferably as a concentration of 10 ⁻⁵ to 10 ⁻² mol. Moreover, it is preferable to adjust pH of aqueous solution to 2-12 from a viewpoint of melt | dissolving a rust preventive agent, pH adjustment is phosphoric acid as buffer as well as usual alkalis and acids, such as sodium hydroxide and a sulfuric acid. Or a salt thereof, carbonate, acetic acid or a salt thereof, boric acid or a salt thereof, or the like can be used.

[Functional membrane]
The translucent electromagnetic wave shielding film of the present invention may be provided with a functional transparent layer having a desired function, if necessary. For example, display panel applications include infrared-shielding layers composed of infrared-absorbing compounds and metals; hard-coating layers that are not easily scratched; antireflection with antireflection properties adjusted for refractive index and film thickness Non-glare layer or anti-glare layer having antiglare properties such as a glare prevention function; a layer for preventing static electricity; an antifouling layer having a function for easily removing dirt such as fingerprints; a layer for cutting ultraviolet rays; a gas barrier A layer having a property; for example, a display panel breakage preventing layer having a function of preventing glass scattering when glass is broken can be provided. These functional layers may be provided on the conductive metal part, or may be provided on the opposite side of the conductive metal part via a transparent substrate.

  Some of the functional transparent layers will be further described.

The layer having infrared shielding properties, for example, the near infrared absorbing layer is a layer containing a near infrared absorbing dye such as a metal complex compound, or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on the substrate by sputtering or the like. The dielectric layer includes a transparent metal oxide such as indium oxide or zinc oxide as a dielectric. The metal contained in the metal layer is generally silver or a silver-palladium alloy. The sputtered silver layer generally has a structure in which about 3, 5, 7 or 11 layers are laminated, starting from the dielectric layer.
In the PDP, the phosphor that emits blue light has a characteristic of emitting red light in addition to blue, but has a problem that a portion to be displayed in blue is displayed in a purplish color. . The layer having a color tone adjusting function that absorbs visible light in the specific wavelength range is a layer that corrects the colored light as a countermeasure, and contains a dye that absorbs light in the vicinity of 595 nm.

  As a method of forming an antireflection layer imparted with antireflection properties, metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides are used in order to suppress reflection of external light and suppress a decrease in contrast. A method of laminating an inorganic substance such as a single layer or multiple layers by a vacuum deposition method, a sputtering method, an ion plating method, or an ion beam assist method, or a single layer or a resin having a different refractive index such as an acrylic resin or a fluororesin There is a method of laminating on a functional layer in multiple layers. Moreover, the film which gave the antireflection process can also be affixed on a film | membrane.

  As a method for forming the non-glare layer or the anti-glare layer, a method of forming a fine powder such as silica, melamine, or acrylic into an ink and coating the surface can be used. At this time, the ink can be cured by thermal curing or photocuring. In addition, a film that has been subjected to non-glare treatment or anti-glare treatment can be attached to the film.

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 antireflection layer and / or the antiglare layer is formed on the hard coat layer, a functional film having scratch resistance, antireflection property and / or antiglare property is preferably obtained.
The surface hardness of the translucent electromagnetic wave shielding film to which hard coat properties are imparted is preferably a pencil hardness according to JIS (K-5400) of at least H, more preferably 2H, and even more preferably 3H or more. .

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 light-transmitting 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.

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.).

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 ultraviolet cut-off properties can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate. 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 cut-off 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.

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 pigment deterioration and fogging, 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.

  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 said to have insufficient color reproducibility. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm, and has a relatively strong short wavelength. There is a problem in that red emission is not good in color purity close to orange due to the emission peak on the side. 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 it contains 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. 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.

When the translucent electromagnetic wave shielding film having the functional film attached thereto is attached to the display, it is usually attached so that the functional film is on the outside and the adhesive layer is on the display side.
Here, it is desirable to ground the conductive metal part in order not to deteriorate the electromagnetic wave shielding ability of the translucent electromagnetic wave shielding film. 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 make good electrical contact with the ground part of the display body, It is preferable that it is not patterned like a metal foil solid.

  The conductive portion may be a mesh pattern layer or an unpatterned layer of metal foil, for example, but the metal foil solid layer may be used for good electrical contact with the ground portion of the display body. It is preferable that the conductive portion is not patterned like a layer.

  For example, when the conductive part is not patterned like a solid metal foil and / or when the conductive part has a sufficiently strong mechanical strength, the conductive part itself can be used as an electrode.

In order to protect the conductive part and / or to make good electrical contact with the ground part when the conductive part is a mesh pattern layer, it may be preferable to form an electrode on the conductive part. The electrode shape is not particularly limited, but is preferably formed so as to cover all the conductive portions.
The material used for the electrode is a single element or an alloy of two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. Alternatively, a paste made of a synthetic resin and a mixture of these simple substances or alloys, or a paste made of borosilicate glass and a mixture of these simple substances or alloys can be used. Conventionally known methods can be employed for printing and coating the paste. Moreover, a commercially available conductive tape can also be used conveniently. The conductive tape has conductivity on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used. The thickness of the electrode is not particularly limited, but is about several μm to several mm.

[Easily adhesive layer]
The preferable easily bonding layer of this invention is demonstrated. The easy adhesion layer may be composed of one layer, or may be composed of two or more layers.
In the present invention, it is preferable to provide an easy-adhesion layer having the following two-layer structure on the surface on the side where the fine mesh wire is provided on the transparent substrate.
(composition)
First layer: Antistatic layer with water-dispersible or water-soluble synthetic resin, carbodiimide compound and conductive metal oxide particles as essential components Second layer: Water-dispersible or water-soluble synthetic resin, and cross-linking agent as essential components Surface layer (It is not the surface layer when laminated with other constituent layers, but it means the top layer of the easy-adhesion layer)
The easy adhesion layer is provided with an antistatic layer and a surface layer in this order on a transparent substrate. In the antistatic layer in the present invention, the haze of the low chargeable transparent substrate obtained by providing the antistatic layer on the transparent substrate is 3% or less, and the surface electrical resistance of the surface layer is 8 × 10 ⁶ to Conductivity is imparted so as to be in the range of 6 × 10 ⁸ Ω. By providing the antistatic layer, it is possible to suppress the occurrence of trouble with dust caused by static electricity that occurs in the manufacturing process of handling the transparent substrate.
In addition, the haze as used in the present specification is a value measured according to JIS K-6714 using a haze meter (HGM-2DP, Suga Test Instruments) under measurement conditions of 25 ° C. and 60% RH.

  The antistatic layer is a layer containing conductive metal oxide particles, and generally further contains a binder. The conductive metal oxide particles are preferably acicular particles having a major axis to minor axis ratio (major axis / minor axis) in the range of 3 to 50. In particular, those having a major axis / minor axis in the range of 10 to 50 are preferable. The minor axis of such acicular particles is preferably in the range of 0.001 to 0.1 μm, and particularly preferably in the range of 0.01 to 0.02 μm. The major axis is preferably in the range of 0.1 to 5.0 μm, and particularly preferably in the range of 0.1 to 2.0 μm.

Examples of the material of the conductive metal oxide particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO _3, and complex oxides thereof, and metal oxides thereof. Further, metal oxides containing different atoms can be given. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₂ and TiO ₂ are preferable, and SnO ₂ is particularly preferable. . Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. When the added amount exceeds 30 mol%, the degree of blackening of the particles increases, and the charge is increased. The prevention layer is dark and not suitable. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure. As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%. Therefore, in the present invention, it is advantageous to use a metal oxide particle such as antimony-doped SnO ₂ having the dimensions of the short axis and the long axis in order to form an antistatic layer that is transparent and has good conductivity. is there. As a result, a material having a low chargeable transparent substrate having a haze of 3% or less and a surface layer having a surface electrical resistance in the range of 8 × 10 ^{6 to} 6 × 10 ⁸ Ω can be easily obtained.

About the reason why an antistatic layer which is transparent and has good conductivity can be advantageously formed by using acicular metal oxide particles having the dimensions of the short axis and the long axis (eg, antimony-doped SnO ₂ ). Is considered as follows. In the antistatic layer, the needle-like metal oxide particles extend long in the major axis direction parallel to the surface of the antistatic layer, but the length of the minor axis in the thickness direction of the layer. It only occupies. Since such acicular metal oxide particles are long in the major axis direction as described above, they are easier to contact with each other than ordinary spherical particles, and high conductivity can be obtained even in a small amount. Accordingly, the surface electrical resistance can be reduced without impairing the transparency. Further, in the needle-like metal oxide particles, the minor axis diameter is usually smaller than or substantially the same as the thickness of the antistatic layer and rarely protrudes on the surface. Therefore, it is almost completely covered by the surface layer provided on the antistatic layer. Therefore, the advantage that there is almost no occurrence of powder falling, which is the detachment of the protruding portion from the layer, during the conveyance of the transparent base material can be obtained.

  The antistatic layer in the present invention generally contains a binder for dispersing and supporting the conductive metal oxide particles. As a material for the binder, various polymers such as an acrylic resin, a vinyl resin, a polyurethane resin, and a polyester resin can be used. From the viewpoint of preventing powder falling, a cured product of a polymer (preferably an acrylic resin, a vinyl resin, a polyurethane resin, or a polyester resin) and a carbodiimide compound is preferable. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use either a water-soluble polymer or a carbodiimide compound, or an aqueous dispersion such as an emulsion. Further, the polymer has any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with the carbodiimide compound is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of hydroxyl group or carboxyl group in the polymer is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  Acrylic resins include acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid esters such as methacrylic acid and alkyl methacrylate, and homopolymers of any monomer of methacrylamide and methacrylonitrile. Or the copolymer obtained by superposition | polymerization of 2 or more types of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can. The acrylic resin has the above composition as a main component and, for example, partially uses a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a carbodiimide compound is possible. The resulting polymer.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ( A meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer). Is preferred. The vinyl resin can be crosslinked with a carbodiimide compound so that, for example, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate leave a vinyl alcohol unit in the polymer. Thus, the polymer having a hydroxyl group is used, and the other polymer is, for example, a crosslinkable polymer by partially using a monomer having any of a methylol group, a hydroxyl group, a carboxyl group, and an amino group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carbodiimide compound.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the above-mentioned polyester resin, for example, the hydroxyl group and carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of crosslinking reaction with the carbodiimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

  Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

As the carbodiimide compound used in the present invention, a compound having a plurality of carbodiimide structures in the molecule is preferably used.
Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. Here, the organic group of the organic diisocyanate used for the synthesis of the compound having a plurality of carbodiimide structures in the molecule is not particularly limited, and either aromatic or aliphatic, or a mixed system thereof can be used. An aliphatic system is particularly preferred from the viewpoint of reactivity.
As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.
Moreover, the carbodiimide type compound that can be used in the present invention is also available as a commercial product such as Carbodilite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).
The carbodiimide compound is preferably added in an amount of 1 to 200% by weight, more preferably 5 to 100% by weight, based on the binder.

  To form the antistatic layer in the present invention, first, for example, a dispersion in which the conductive metal oxide particles are dispersed as they are or in a solvent such as water (including a dispersant and a binder as necessary) An antistatic layer-forming coating solution is prepared by adding and mixing (dispersing as necessary) an aqueous dispersion or aqueous solution containing the binder (eg, polymer, carbodiimide compound and appropriate additive). The antistatic layer is formed by applying a coating solution for forming the antistatic layer on a transparent substrate, such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, or a gravure coating method. It can be applied by an extrusion coating method or the like. The plastic film such as polyester to be applied may be any of before sequential biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching and before re-stretching, or after biaxial stretching. The surface of the transparent substrate to which the antistatic layer-forming coating solution is applied is preferably subjected to a surface treatment such as an ultraviolet irradiation treatment, a corona discharge treatment, or a glow discharge treatment in advance.

  The layer thickness of the antistatic layer in the present invention is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If the coating agent is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior. The conductive metal oxide particles are preferably contained in the antistatic layer in the range of 10 to 1000% by mass with respect to the binder (eg, the total of the polymer and the carbodiimide compound), and more preferably 100 to 500%. A range of mass% is preferred. If it is less than 10% by mass, sufficient antistatic properties cannot be obtained, and if it exceeds 1000% by mass, the haze becomes too high.

  In the present invention, the antistatic layer and the following surface layer can be used in combination with additives such as a matting agent, a surfactant and a slipping agent, if necessary. Examples of the matting agent include particles of oxides such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, and particles of a polymer or a copolymer such as polymethyl methacrylate and polystyrene. Can do. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Examples of slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds. Can do.

  In the present invention, a surface layer may be provided on the antistatic layer. The surface layer is provided mainly to assist the adhesion imparting with the adhesive layer and the anti-detachment function of the conductive metal oxide particles of the antistatic layer. As the material for the surface layer, various polymers such as acrylic resin, vinyl resin, polyurethane resin, and polyester resin can be generally used, and polymers described as the binder in the antistatic layer are preferable.

The cross-linking agent used for the surface layer is preferably an epoxy compound that does not affect the mesh-like fine wires that are contacted when the roll is wound in the manufacturing process.
Examples of the epoxy compound include 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-acetoxy-β-oxy Propyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol poly Epoxy compounds such as glycerol ethers and trimethylolpropane polyglycidyl ethers are preferable, and specific examples of commercially available products include Denacol EX-521 and EX-614B (manufactured by Nagase Chemical Industries). Although it is not intended to be limited thereto.
Further, it can be used in combination with other crosslinkable compounds, for example, “The Theory of the Photographic Process” by CEKMeers and THJames, 3rd edition (1966), US Pat. Nos. 3,316,095, 3,32,764 and 3,288,775, No. 2,732,303, No. 3,635,718, No. 3,323,763, No. 2,732,316, No. 2,586,168, No. 3,103,437, No. 3,307,280, No. 2,983611, No. 2,725,294, No. 2,725,295, No. 3,100,704, No. 3,091,537, and No. 3321313 , Nos. 3543292 and 3125449, and British Patent Nos. 994869 and 1167207, and the like.
As a typical example, a melamine compound containing at least one of two or more (preferably three or more) methylol groups and an alkoxymethyl group or a condensation polymer thereof, a melamine resin or a melamine urea resin, Mucochloric acid, mucobromic acid, mucofenoxycyclolic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglioxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4 Aldehyde compounds such as dioxane succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde and derivatives thereof; divinylsulfone-N, N′-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2 - Lopanol, methylene bismaleimide, 5-acetyl-1,3-diaacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro- active vinyl compounds such as s-triazine; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2,4- Active halogen compounds such as dichloro-6- (2-sulfoethylamino) -s-triazine and N, N′-bis (2-chloroethylcarbamyl) piperazine; bis (2,3-epoxypropyl) methylpropylammonium P-toluenesulfonate, 2,4,6-triethylene-s-triazine, 1, Ethyleneimine compounds such as 6-hexamethylene-N, N′-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di (methanesulfoneoxy) ethane, 1,4-di (methanesulfoneoxy) ) Methanesulfonic acid ester compounds such as butane and 1,5-di (methanesulfonoxy) pentane; carbodiimide compounds such as dicyclohexylcarbodiimide and 1-dicyclohexyl-3- (3-trimethylaminopropyl) carbodiimide hydrochloride; 2,5 -Isoxazole compounds such as dimethylisoxazole; inorganic compounds such as chromium alum and chromium acetate; N-carboethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy) -4 -Removal of methylpyridium chloride, etc. Condensation type peptide reagents; active ester compounds such as N, N′-adipoyldioxydisuccinimide and N, N′-terephthaloyldioxydisuccinimide: toluene-2,4-diisocyanate and 1,6-hexa Examples thereof include, but are not limited to, isocyanates such as methylene diisocyanate; and epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reactant.

  For the formation of the surface layer, first, the polymer, epoxy compound, and appropriate additive are added to a solvent such as water (including a dispersant and a binder as necessary) and mixed (dispersed if necessary). To prepare a surface layer coating solution.

  The surface layer is formed on the antistatic layer in the present invention by a generally well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, and extrusion coating. It can form by apply | coating the said surface layer coating liquid. The layer thickness of the surface layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If it is less than 0.01 μm, the anti-detachment function of the conductive metal oxide particles of the antistatic layer is insufficient, and if it exceeds 1 μm, it is difficult to uniformly apply the coating agent, and uneven coating tends to occur on the product.

[Adhesive layer]
The adhesive layer preferably used in the present invention will be described.
The translucent electromagnetic wave shielding film of the present invention is bonded via an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display panels, or the like.

  The refractive index of the adhesive used in the present invention is preferably 1.40 to 1.70. This is because the difference between the transparent base material such as a plastic film used in the present invention and the refractive index of the adhesive is reduced to prevent the visible light transmittance from being lowered. When it is .40 to 1.70, the decrease in visible light transmittance is small and good.

The adhesive used in the present invention is preferably an adhesive that flows by heating or pressurization, and in particular, fluidity by heating at 200 ° C. or less or pressurization at 1 kgf / cm ² (0.098 MPa) or more. It is preferable that it is an adhesive which shows. Since it can flow, a translucent electromagnetic shielding film (electromagnetic shielding adhesive film) having an adhesive layer can be bonded to an adherend by lamination or pressure molding, particularly pressure molding. Further, it can be easily bonded to an adherend having a curved surface or a complicated shape. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or higher, and most preferably 80 to 120 ° C. in view of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poises or less, and normally, the flow is recognized within a time of 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, diglycidyl adipate, diglycidyl phthalate, 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. The softening temperature of the polymer used as these adhesives is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C. or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. in view of processability. On the other hand, it is preferable to use a polymer having a mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same applies hereinafter) of 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. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, a coloring agent, a ultraviolet absorber, and a tackifier, with the adhesive agent used by this invention as needed. The thickness of the adhesive layer is preferably 10 to 80 μm, particularly preferably 20 to 50 μm.

  The adhesive layer has a refractive index difference of 0.14 or less with respect to the transparent substrate. By satisfying this difference in refractive index, the decrease in visible light transmittance is small and good. As an adhesive material satisfying such requirements, when the transparent substrate is polyethylene terephthalate (n = 1.575; refractive index), bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrahydroxyphenylmethane type epoxy resin, Novolac epoxy resin, resorcinol type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as cycloaliphatic or halogenated bisphenol (all with a refractive index of 1.55 to 1.60) can be used . Other than epoxy resin, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.5125), 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 = 1.4563), polyoxypropylene (n = 1.4495), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.4591), polyvinyl butyl ether (n = 1.4563) Ethers, polyesters such as polyvinyl acetate (n = 1.4665), polyvinyl propionate (n = 1.4665), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.5 4-1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), etc. Can do. These express suitable visible light transmittance.

In addition, acrylic resins are well known as those that hardly change color over time, and are preferably used in the present invention. Examples include polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly-t-butyl acrylate (n = 1.4638), poly-3- Ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethacrylate (n = 1.465), polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.4728), polydodecyl methacrylate (n = 1.474), poly Tetradecyl methacrylate (n = 1.4746), 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 = 1.4868), polytetracarbanyl Poly (meth) acrylic acid esters such as acrylate (n = 1.4889), poly-1,1-diethylpropyl methacrylate (n = 1.4889), polymethyl methacrylate (n = 1.4893), acrylic acid and methacrylic acid can be used. It is. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used.
By blending a plurality of types of acrylic polymers having different molecular weights, it is possible to adjust the viscoelasticity of the adhesive to a desired property.

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

  Adhesive curing agents include amines such as triethylenetetramine, xylenediamine, and diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride, Diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the 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. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the adhesive agent used by this invention as needed. The adhesive resin composition is applied to cover a part or the entire surface of the easy-adhesion layer, followed by solvent drying and heat-curing steps to obtain an electromagnetic wave shielding adhesive film. The electromagnetic wave shielding adhesive film obtained above is used by directly attaching to a display such as a CRT, PDP, liquid crystal, EL or the like, or by attaching it to a plate or sheet such as an acrylic plate or a glass plate. Moreover, this electromagnetic wave shielding adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring device, measuring device or manufacturing device that generates electromagnetic waves. Furthermore, it is provided in a window of a building or a window of an automobile that may be affected by an electromagnetic wave interference by a radio tower or a high voltage line. And it is preferable to provide a ground wire in the mesh-like thin wire as described above.

  Even when the transparent substrate has irregularities and has haze to scatter light, if the resin with a refractive index close to that of the transparent substrate is smoothly applied to the uneven surface or the resin sheet is laminated, diffuse reflection Is minimized, and transparency is developed. Further, the mesh-like fine line of the present invention is not visually recognized by the naked eye because the line width is very small. Moreover, since the pitch is sufficiently large, it is considered that apparent transparency is expressed. On the other hand, since the pitch of the geometric figure is sufficiently smaller than the wavelength of the electromagnetic wave to be shielded, it is considered that excellent shielding properties are exhibited.

  In general, the surface of the display is made of glass, so bonding with an adhesive is a bonding between a transparent substrate and a glass plate, and bubbles are formed or peeled off on the bonding surface. Problems occur such as the image being distorted and the display color appearing different from the original display. Moreover, the problem of bubbles and peeling occurs in any case when the adhesive peels off from the plastic film or glass plate. This phenomenon may occur on both the transparent substrate side and the glass plate side, and peeling occurs on the side with weaker adhesion. Therefore, it is necessary that the adhesive force between the adhesive at high temperature, the transparent substrate, and the glass plate is high. Specifically, the adhesion between the transparent transparent substrate and the glass plate and the adhesive layer is 80 when the peel strength when measured in the direction of 180 degrees with respect to the joint surface at a pulling speed of 100 mm / min is 80. It is preferably 10 g / cm (10 N / m) or more at ° C. It is more preferably 20 g / cm (20 N / m) or more, and particularly preferably 30 g / cm (30 N / m) or more. However, an adhesive exceeding 2000 g / cm (2 kN / m) may not be preferable because the bonding operation becomes difficult. However, if this problem does not occur, it can be used without problems. Furthermore, it is also possible to provide a slip sheet (separator) so that the portion of the adhesive that does not face the transparent substrate does not unnecessarily come in contact with other portions.

  The adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that the degree of purity is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable. The adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, it can be considered substantially colorless if the adhesive is thin. Similarly, when intentionally coloring as described later, it is not within this range.

  Examples of the adhesive having the above characteristics include acrylic resins, α-olefin resins, vinyl acetate resins, acrylic copolymer resins, urethane resins, epoxy resins, vinylidene chloride resins, vinyl chloride resins, Examples thereof include ethylene-vinyl acetate resin, polyamide resin, and polyester resin. Of these, acrylic resins are preferred. Even when the same resin is used, the adhesiveness can be reduced by reducing the addition amount of the crosslinking agent, adding a tackifier, or changing the end group of the molecule when synthesizing the adhesive by the polymerization method. It is also possible to improve. Even when the same adhesive is used, it is possible to improve the adhesion by modifying the surface on which the adhesive is bonded, that is, the surface of the transparent substrate or the glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.

  From the viewpoint of transparency, colorlessness, and handling properties, the thickness of the adhesive layer is preferably about 5 to 50 μm. In the case where the adhesive layer is formed of an adhesive, the thickness may be reduced within the above range. Specifically, it is about 1 to 20 μm. However, when the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.

(Peel strength)
The adhesion strength of the film provided with the adhesive layer on the easy-adhesive layer in the present invention with the glass substrate is preferably as follows.
When the peel strength is measured when the film sample is attached to a glass substrate and pulled in the direction of 180 degrees with respect to the joint surface at a pulling speed of 100 mm / min, the peel strength is preferably 20 N / m or more. Furthermore, it is preferable that the peel strength is 20 N / m or more under the above-described tensile conditions after aging for 75 hours at 60 ° C. and a relative humidity of 90%.

[Light transmission part]
The “light transmitting part” in the present invention means a part having transparency other than the conductive metal part in the light transmitting electromagnetic wave shielding film. As described above, the transmittance in the light transmissive part is 90% or more, preferably the transmittance indicated by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the transparent substrate. 95% or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.

  The translucent electromagnetic wave shielding film of the present invention can be provided with a peelable protective film. The protective film does not need to be provided on both surfaces of the translucent electromagnetic wave shielding film, and can be provided only on the mesh-like thin wire or only on the opposite side. When the protective film is provided on a mesh-like fine wire, 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, There is a possibility that the fine mesh wire may peel off from the transparent substrate (or from the easy adhesion layer), which is also not preferable.

  As the film constituting the protective film, it is preferable to use a polyolefin resin such as polyethylene resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, resin film such as polycarbonate resin or acrylic resin, and adhesion of the protective film. The surface to be treated is preferably subjected to corona discharge treatment.

  Moreover, as an adhesive which comprises a protective film, an acrylate ester type | system | group, a rubber type, or a silicone type thing can be used.

[Blackening layer]
The translucent electromagnetic wave shielding film of the present invention may be subjected to blackening treatment.
The blackening process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576. The blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antirust effect. The blackened layer can be formed by, for example, Co—Cu alloy plating, and reflection of the surface can be prevented by providing the blackened layer on the conductive metal portion. Further, a chromate treatment may be performed thereon as a rust prevention treatment. The chromate treatment is performed by dipping in a solution containing chromic acid or dichromate as a main component and drying to form a rust-preventive coating, which can be performed on one or both sides of the conductive metal portion as necessary. it can.

  Further, as another example of the configuration including the blackening layer, the configuration described in JP-A-11-266095 may be used. That is, the first blackening layer is provided on the conductive metal portion, the electrolytic plating is performed on the first blackening layer, and then the second blackening layer is further provided on the plating. is there. In order to perform electroplating on the first blackened layer, at least the first blackened layer needs to be conductive. In general, the conductive blackening layer can be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using an ionic polymer material such as an electrodeposition coating material.

A method of providing a blackened layer is known (for example, see FIG. 5 of JP-A-11-266095). For example, a transparent base material on which a conductive metal portion is formed may be immersed in an electrolytic solution containing a blackening material and plated by an electrochemical plating method. In the present invention, the electrolytic solution bath (black plating bath) containing the blackening material can be a black plating bath mainly composed of nickel sulfate, and is a commercially available black plating bath. Specifically, for example, a black plating bath manufactured by Shimizu Co., Ltd. (trade name, Novroi SNC, Sn—Ni alloy system), a black plating bath manufactured by Nippon Chemical Industry Co., Ltd. (Trade name, Nikka Black, Sn—Ni alloy system), black plating bath (trade name, Ebony-Chromium 85 series, Cr system) manufactured by Metal Chemical Co., Ltd., etc. can be used. Moreover, in this invention, various black plating baths, such as Zn type | system | group, Cu type | system | group, others, can be used as said black plating bath. Next, the conductive plating is performed to form a mesh pattern, and then a second blackening layer is formed thereon. For example, when the electroplating metal is Cu, a hydrogen sulfide (H ₂ S) solution treatment is performed to blacken the Cu surface as copper sulfide (CuS), thereby forming a second blackened layer. In the present invention, as the blackening treatment agent for the second blackening layer, it can be easily produced using a sulfide-based compound, and there are also various types of treatment agents on the market, for example, Product name: Copa Black CuO, CuS, Selenium Copa Black No. 65 (made by Isolate Chemical Laboratories, Inc.), trade name, Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used.

  Since the translucent electromagnetic shielding film of the present invention has good electromagnetic shielding and translucency, it can be applied to the front of displays such as CRT, PDP, liquid crystal, and EL, microwave ovens, electronic equipment, and printed wiring boards. And is particularly useful for PDPs. In particular, according to the present invention, it is possible to obtain an optical filter having excellent optical characteristics that can maintain or improve the image quality without significantly impairing the brightness of the plasma display. In addition, it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health generated from plasma displays, and it also efficiently uses near-infrared rays near 800 to 1000 nm emitted from plasma displays. Since it is cut well, an optical filter that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof can be obtained. Furthermore, an optical filter having excellent weather resistance can be provided at a low cost.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1
A transparent substrate was prepared as described below, and an easy-adhesion layer was provided on both sides thereof, and then a silver paste was printed to obtain a plastic film having a mesh pattern.

<Transparent substrate>
Polyethylene terephthalate (PET) resin having an intrinsic viscosity of 0.66 obtained by polycondensation using antimony trioxide as a main catalyst was dried to a water content of 50 ppm or less and melted in an extruder set at a heater temperature of 280 to 300 ° C.
The melted PET resin was discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous base. The obtained amorphous base was stretched 3.1 times in the base traveling direction and then stretched 3.9 times in the width direction to obtain a transparent substrate having a thickness of 96 μm.

<Creation of silver paste>
In accordance with a method for preparing a Carey-Lea silver sol (see M. Carey Lea, Brit. J. Photog., Vol. 24, p. 297 (1877) and Vol. 27, p. 279 (1880)) After preparing silver fine particles, a chloroauric acid solution was added to prepare silver gold fine particles containing silver as a main component, and ultrafiltration was performed to remove by-produced salts. As a result of observation with an electron microscope, the particle size of the obtained fine particles was approximately 10 nm.
The particles were mixed with a solvent containing methyl ethyl ketone and a binder made of an acrylic resin to prepare a paste.

<Silver paste printing>
Using the transparent base material obtained as described above, a silver paste was printed thereon by an intaglio printing method using a roll-shaped plate cylinder. The sample length was 100 m.
Subsequently, it heat-processed at 130 degreeC for 10 minutes. The obtained mesh pattern was a silver lattice mesh having a line width of 18 μm and a pitch of 300 μm.
Next, a linear pressure of 2940 N / cm (300 kgf / cm) was applied with a calender roll, the sample was passed between calender rollers composed of two pairs of metal rolls, and the mesh pattern was calendered.

<Easily adhesive layer: Back layer>
In the sample used in the present invention, a coating solution having the following composition was sequentially applied and dried under the following coating conditions to form a back layer.
In a state where the transparent base material is transported at a transport speed of 105 m / min, the surface of the base material is subjected to corona discharge treatment under a condition of 727 J / m ² , and an antistatic layer coating liquid having the following composition is applied by a bar coating method. Applied.
The coating amount was 7.1 cc / m ² and an antistatic layer was obtained by drying at 180 ° C. for 1 minute in an air floating drying zone.
(Coating solution for antistatic layer)
Distilled water 781.7 parts by mass Polyacrylic resin (Julimer ET-410: Nippon Pure Chemical Co., Ltd., solid content 30%) 30.9 parts by mass Acicular structure tin oxide particles (FS-10D: Ishihara Sangyo Co., Ltd., solid content 20%) 131.1 parts by mass Carbodiimide compound (Carbodilite V-02-L2: Nisshinbo, solid content 40%) 6.4 parts by mass surfactant (Sandet BL: Sanyo Chemical Industries solid content 44.6%) 1.4 parts by mass surfactant (Naroacty HN-100: Sanyo Kasei Kogyo Co., Ltd., solid content 100%) 0.7 parts by mass Silica fine particle dispersion (Seahoster KE-W30: Nippon Shokubai 0.3 μm solid content 20%) 5.0 parts by mass

While maintaining the conveyance speed of 105 m / min, a surface layer coating solution having the following composition was subsequently applied by bar coating on the above-described antistatic property.
The coating amount was 5.05 cc / m ^2, and a back layer having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air floating drying zone.

(Coating solution for surface layer)
Distilled water 941.0 parts by mass Polyacrylic resin (Julimer ET-410: manufactured by Nippon Pure Chemicals, solid content 30%) 57.3 parts by mass epoxy compound (Denacol EX-521: manufactured by Nagase Chemical Industries, solid content 100%) 1.2 parts by mass Agent (Sandet BL: Sanyo Chemical Industries, solids 44.6%) 0.5 parts by mass

<Easily-adhesive layer: Easy-adhesive layer on the fine wire side of the mesh shape>
An easy-adhesion layer was applied on the opposite side of the backing layer from the backing layer by the same method except that no acicular structure tin oxide particles were contained.

<Electrolytic plating>
After the silver paste printing, a conductive film in which the conductive metal portion is made of silver and copper was prepared by performing a plating process using the following plating solution. In addition, the surface resistance value of the film before electrolytic plating was 8Ω / □.

・ Plating treatment Acid cleaning 35 ° C. 30 seconds Electrolytic plating 1 35 ° C. 30 seconds Electrolytic plating 2 35 ° C. 30 seconds Electrolytic plating 3 35 ° C. 30 seconds Electrolytic plating 4 35 ° C. 30 seconds Rinse 3 * 35 ° C. 10 seconds Rinse 4 * 35 ° C. 10 Second Antirust solution 35 ° C 30 seconds Rinse 5 * 25 ° C 60 seconds Rinse 6 * 25 ° C 60 seconds Drying 50 ° C 60 seconds
* The water-washing process was a two-tank counter-flow system from rinse 2 to 1, rinse 4 to 3, and rinse 6 to 5.
[Electrolytic plating solution 1L prescription]
・ Electrolytic copper plating solution composition (same replenisher composition)
Copper sulfate pentahydrate 75 g
190 g of sulfuric acid
Hydrochloric acid (35%) 0.06 mL
Capper Gream PCM 5 mL
(Rohm and Haas Electronic Materials Co., Ltd.)
Add pure water and add 1 L

[Rinse solution 1L prescription (Rinse 1-6 are common)]
Deionized water (conductivity 5μS / cm or less) 1000 mL
Adjusted to pH 6.5

Further, an antirust treatment was performed with an aqueous solution containing benzotriazole (0.01 mol / L). The rust prevention treatment was performed by immersing in the above aqueous solution for 3 minutes.
After the rust prevention treatment, the sample was washed with water and dried to obtain a sample of the present invention.

(Examples 2 and 3 and Comparative Example 1)
Various samples were prepared under the conditions shown in Table 1.

<Evaluation method>
(Surface resistance)
The surface resistivity was measured using a Mitsubishi Chemical Corporation low resistivity meter, Lorester GP / ASP probe.
(surface hardness)
A scratch test using a pencil based on the JIS pencil hardness test method was performed, and “X” indicates that the pattern portion made of silver is dropped, and “◯” indicates that the pattern portion is not dropped.
(Evaluation of peel strength)
A sheet-like acrylic adhesive was affixed to the easy-adhesion layer side on the mesh-like pattern side of each sample, and was affixed to a glass substrate.
The 180 ° peel strength indicated above was measured. All samples showed a peel strength of 20 N / m or more. Further, after storing for 75 hours at 60 ° C. and 90% humidity, the 180 ° peel strength was also measured.
The evaluation results are shown in Table 1.

  As can be seen from Table 1, the samples of the examples of the present invention exhibited good conductivity (low surface resistivity) by electrolytic plating, and the peel strength after wet heat aging was also good. However, since the sample of Example 2 was not provided with an easy-adhesion layer on the mesh-like fine wire side, the results were slightly inferior in terms of surface hardness and peel strength after wet heat aging.

Example 4
(Production of optical filter)
Using the sample obtained in Example 1, a glass plate was bonded to the inner light-transmitting electromagnetic wave shielding film excluding the outer edge portion of 20 mm via an acrylic light-transmitting adhesive material having a thickness of 25 μm. The acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the optical filter. Furthermore, an antireflection film having a near-infrared cutting ability (trade name: Realak 772UV, manufactured by NOF Corporation) was bonded to the opposite main surface of the glass plate via an adhesive material to produce an optical filter.

  The obtained optical filter has a black metal mesh, and when this is used for a plasma display panel, the display image does not have a metallic color, and has an electromagnetic shielding ability and a near infrared ray cutting ability that are not problematic in practice. And had excellent visibility due to the antireflection layer. Further, by adding a dye, a color-adjusting function can be imparted, and it can be suitably used as an optical filter such as a plasma display.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electroplating tank 11 Plating bath 12a, 12b Feed roller 13 Anode plate 14 Guide roller 15 Plating solution 16 Film 17 Liquid removing roller

Claims (11)

  A translucent electromagnetic wave shielding film in which a fine mesh wire having a line width of 1 μm to 30 μm mainly composed of silver is formed on a transparent substrate, wherein the fine mesh wire is first formed on the transparent substrate The mesh-like pattern is obtained by further electroplating after forming a mesh-like pattern by printing, and the mesh-like fine line is 3 m in the longitudinal direction of the translucent electromagnetic shielding film. A translucent electromagnetic wave shielding film characterized by being continuous as described above.   The surface resistance of the transparent substrate after forming a mesh-like pattern by the printing is 1Ω / □ to 100Ω / □, and then continuous electroplating is applied to the mesh-like pattern. 2. The translucent electromagnetic wave shielding film according to 1.   3. The translucent electromagnetic wave shielding film according to claim 1, wherein after the mesh pattern is formed by the printing, the mesh pattern is calendered.   The translucent electromagnetic wave shielding film according to claim 3, wherein the calendar treatment is performed at a linear pressure of 1960 N / cm (200 kgf / cm) or more.   The translucent electromagnetic wave shielding film according to any one of claims 1 to 4, wherein the mesh-like fine wire contains a rust preventive agent.   The translucent electromagnetic wave shielding film according to claim 1, wherein an easy adhesion layer is provided between the transparent base material and the mesh-like fine wire.   The adhesive layer is provided on the easy-adhesion layer so that the peel strength of the adhesion through the easy-adhesion layer between the transparent base material and the glass substrate is 20 N / m or more. Translucent electromagnetic shielding film.   The translucent electromagnetic wave shielding film according to claim 7, wherein the peel strength after being left for 75 hours at 60 ° C. and a humidity of 90% or more is 20 N / m or more.   The translucent electromagnetic wave shielding film according to claim 1, wherein the electrolytic plating is a plating treatment for plating at least one selected from copper, nickel, zinc, tin, and cobalt.   An optical filter comprising the translucent electromagnetic wave shielding film according to claim 1.   A plasma display panel comprising the translucent electromagnetic wave shielding film according to claim 1.

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