JP2009016700A - Mesh metal particle laminated board and method for manufacturing transparent conductive board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a method for manufacturing a mesh metal particle laminated board, by which the mesh metal laminated board excellent in transparency and moire-proof property can be manufactured to eliminate defects such as a stripe and flaw in a coating film; a mesh metal particle laminated board; and a transparent conductive board using the same. <P>SOLUTION: The method for manufacturing a mesh metal particle laminated board is a method for laminating a metal particle layer on a board in a mesh manner by applying metal particle solution to a surface in which the surface wet tension of at least one side of the board is 45 to 73 mN/m, and surface wet tension is 45 to 73 mN/m, wherein the method performs lamination by a noncontact type applying method for preventing at least metal particle solution from coming into contact with the board. In addition, the mesh metal particle laminated board is manufactured by this manufacturing method, and the transparent conductive board uses the mesh metal particle laminated board. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a reticulated metal fine particle laminate substrate having excellent transparency and moiré resistance, a reticulated metal fine particle laminate substrate, and a transparent conductive substrate using the same.

  Transparent conductive substrates are used in various devices as circuit materials, and are used as electromagnetic shielding substrates and solar cell applications.

  The electromagnetic shielding substrate is used for the purpose of suppressing various electromagnetic waves radiated from electronic devices such as home appliances, mobile phones, personal computers, and televisions. Among digital home appliances that are growing rapidly, strong electromagnetic waves are emitted from flat panel displays such as plasma display panels and liquid crystal televisions, and there is concern about the effects on the human body. Since these displays observe images at a relatively short distance and in some cases for a long time, an electromagnetic wave shielding substrate that suppresses these electromagnetic waves is required and has been intensively studied.

In general, a transparent conductive substrate is used for an electromagnetic wave shielding substrate used in a display panel, and various methods are employed for manufacturing a conductive substrate for an electromagnetic wave shielding substrate that is currently used. Yes. For example, a copper foil is bonded to a polyester film, a regular mesh shape is patterned by photolithography, and the copper foil is etched into a mesh shape, thereby creating a mesh-like conductive film whose conductive portion is copper. (See Patent Document 1).
JP 2001-210988 A

  However, the above-described conventional technique has the following problems.

  The method of etching a copper foil described in Patent Document 1 is an excellent method for obtaining a highly accurate mesh shape. However, in the process of laminating a copper foil, a photolithography process, an etching process, etc. In particular, the yield was poor, and there was a problem that product loss in each process was likely to occur. In particular, there are many environmental issues such as the generation of harmful waste liquid in the etching process. Furthermore, if copper foil is used as a material and then the copper foil is etched to increase permeability, it is necessary to dissolve a large part of the copper foil by etching to make a waste liquid, which is an aspect of material recycling. But there were many issues.

  Moreover, since the lattice-like copper foil layer of this board | substrate has a regular structure, it also had the problem that a moire phenomenon generate | occur | produces.

  Here, the moire phenomenon is “a striped pattern generated when overlapping regularly distributed points or lines geometrically”, and according to Kojien, “a point or line is geometrically Stripe pattern that occurs when superposed distributions are superposed. This is likely to occur when a halftone is reproduced using a halftone print as a manuscript. " Pattern occurs. This is because, when a regular pattern such as a grid pattern is provided on the electromagnetic shielding substrate provided on the front surface of the display, it interacts with a regular grid-shaped partition wall that partitions the pixels of each RGB color on the back side of the display. This moire phenomenon occurs. Further, when a regular pattern such as a grid pattern is provided on the electromagnetic wave shield substrate, there is a problem that the moire phenomenon is more likely to occur as the line width of the grid increases.

  In view of the background of the prior art, the present invention provides a method for producing a mesh metal fine particle laminate substrate and a mesh metal fine particle capable of producing a mesh metal fine particle laminate substrate excellent in transparency and moiré resistance with high productivity. It is intended to provide a laminated substrate and a transparent conductive substrate using the same.

  The present invention employs the following means in order to solve such problems. That is, in the method for producing a reticulated metal fine particle laminated substrate of the present invention, the surface wetting tension of at least one surface of the substrate is 45 mN / m or more and 73 mN / m or less, and the surface wetting tension is 45 mN / m or more and 73 mN / m or less. A method for producing a mesh metal fine particle laminated substrate in which a metal fine particle layer is laminated on a substrate by applying a metal fine particle solution to the substrate, and the metal fine particle solution is laminated by a non-contact coating method that does not contact the substrate It is characterized by doing.

  In addition, the reticulated metal fine particle multilayer substrate of the present invention is manufactured by such a manufacturing method, and the transparent conductive substrate of the present invention is such a reticulated metal fine particle multilayer substrate. It is characterized by using.

  According to the present invention, a metal fine particle laminated substrate is formed into a mesh by laminating a metal fine particle solution on a substrate whose surface wetting tension is controlled to 45 mN / m or more and 73 mN / m or less by a non-contact coating method that does not contact the substrate. A reticulated metal fine particle multilayer substrate that is excellent in both transparency and moire resistance and has no defects such as streaks or scratches on the coating film can be obtained by a method with excellent productivity. . In addition, the transparent conductive substrate using the network metal fine particle multilayer substrate of the present invention has transparency and a high level of conductivity, and also has excellent moire resistance. For example, such as a plasma display panel or a liquid crystal television. It can be suitably used for a flat panel display.

  The present invention is a mesh metal that is excellent in both of the above-mentioned problems, that is, transparency and moire resistance, and can produce a mesh metal fine particle multilayer substrate having defects such as streaks and scratches in the coating film with high productivity. A method for manufacturing a fine particle laminated substrate, and a surface that satisfies a specific condition on at least the surface of the substrate on which the metal fine particle solution is applied when producing a laminated substrate by applying a metal fine particle solution to at least one surface of the substrate As a result of processing to wet tension and laminating the metal fine particle solution by a coating method satisfying specific conditions, it has been found that the above problems can be solved at once.

  In the present invention, by first applying the metal fine particle solution to a substrate having a surface wetting tension under a specific condition under a specific condition, a substrate having excellent transparency can be produced without moire and coating defects. Was made.

  The surface wetting tension of the surface of the substrate on which the metal fine particle solution is applied is preferably 45 mN / m or more and 73 mN / m or less, more preferably 50 to 73 mN / m, and further preferably 55 to 73 mN / m. It is. The surface wetting tension of 73 mN / m is a measurement limit value, and when it is less than 45 mN / m, when the metal fine particle solution is applied to the surface of the substrate, the metal fine particle solution does not form a network, A uniform coating film is formed, and there may be a problem that the transparency of the metal fine particle laminated substrate is inferior.

  In order to adjust the surface wetting tension of the surface of the substrate to which the metal fine particle solution is applied to 45 mN / m to 73 mN / m, known methods such as corona discharge treatment and plasma treatment can be used.

  In the present invention, the surface of the substrate is subjected to a hydrophilic treatment by coating with an anchor coat agent or a primer, and the substrate is provided with a hydrophilic treatment layer on at least one side. It is also a preferred embodiment that the surface wetting tension of the surface is set to 45 mN / m or more and 73 mN / m or less.

  The total light transmittance of the network metal fine particle multilayer substrate is preferably 50% or more, more preferably 65% or more, and further preferably 75% or more. If the total light transmittance is less than 50%, there may be a problem in terms of transparency of the network metal fine particle multilayer substrate.

  Such total light transmittance is measured by the following measuring method. That is, in a normal state (23 ° C., relative humidity 65%), the mesh metal fine particle multilayer substrate was allowed to stand for 2 hours, and then measured using a fully automatic direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. The average value measured three times was taken as the total light transmittance of the network metal fine particle laminated substrate. If the total light transmittance is 50% or more, the transparency is good. In the case of a network-like metal fine particle laminated substrate in which a metal fine particle layer is laminated only on one side of the substrate, the measurement is performed by placing the substrate so that light enters from the side on which the metal fine particle layer is laminated.

  In the present invention, when a network structure is formed using a metal fine particle solution, for example, a solid content solution (metal colloid solution) containing particles composed of metal fine particles and an organic component such as a dispersant is used. The method of performing can be used suitably. As the solvent for the metal colloid solution, water and various organic solvents can be used.

  Examples of the method for adjusting the metal fine particles include a chemical method in which metal ions are reduced to metal atoms in a liquid layer and grown into nanoparticles through atomic clusters, or bulk metal is evaporated in an inert gas. Physics of trapping metal in fine particles with a cold trap, physics of breaking metal thin film by heating metal thin film obtained by vacuum deposition on polymer thin film, and dispersing metal nanoparticles in polymer in solid state Or the like can be used.

  In the present invention, a metal fine particle solution that self-assembles can be preferably used as the metal fine particle solution. Here, the “self-organizing metal fine particle solution” means a solution that spontaneously forms a network structure on a substrate when it is applied to one surface of the substrate and left to stand. As such a metal fine particle solution, for example, CE103-7 manufactured by Cima NanoTech can be used.

  The network structure in the network metal fine particle multilayer substrate of the present invention is preferably irregular. That is, when the reticulated metal fine particle multilayer substrate of the present invention is used by being bonded to a plasma display, it is possible to obtain a structure in which the moire phenomenon does not occur by making the reticulated structure irregular.

  Such an irregular network structure is specified by an observation image of a differential interference microscope, and the network structure is in a state where the shape and size of the void portion are irregular in its shape, that is, as an irregular state. Therefore, the portion of the mesh, that is, the shape of the linear portion is not a straight line, but the line thickness is not uniform, that is, an irregular state. An example of an irregular mesh-like structure is shown in FIG. 1, but is not limited to this.

  In the method for producing a reticulated metal fine particle laminated substrate of the present invention, when applying the metal fine particle solution to at least one surface of the substrate, the specific condition that the metal fine particle solution is laminated by a non-contact coating method that does not contact the substrate is set. It is important to meet. The non-contact coating method is not limited as long as it does not contact the substrate, and a known coating method such as a die coating method, an applicator method, a comma coating method, a spray method, a dipping method and the like can be used. When a contact type coating method that contacts the substrate is used when applying the metal fine particle solution, the portion in contact with the substrate is scratched, or the portion in contact with the substrate when the metal fine particle solution is applied Problems such as streaking may occur, which is not preferable.

  Further, when a contact-type coating method is used in which a surface of the substrate having a surface wetting tension of 45 mN / m or more is further subjected to a hydrophilic treatment, the substrate is contacted with the substrate. Is not preferred because it may be scraped off and not reticulated. For example, a mesh-like metal fine particle laminated substrate obtained by laminating a metal fine particle solution using a wire bar that is in contact with the substrate is a portion that does not come into contact with the wire bar along the wire pitch of the wire bar. The size of the gap portion of the network structure is different, the gap is larger at the contacted portion, and the gap is smaller at the non-contact portion. The different large and small voids are alternately arranged in a streak pattern, resulting in a regular pattern, which may cause a moire phenomenon. In addition, a network-like metal fine particle multilayer substrate laminated using a gravure coater that is a contact type for contacting the substrate with the metal fine particle solution is in contact with the substrate so that the metal fine particle solution has a gravure plate shape. It may be applied and a gravure plate may be formed. Therefore, it is necessary to apply the metal fine particle solution by a non-contact application method that does not contact the substrate.

  In the method for producing a reticulated metal fine particle laminated substrate of the present invention, when applying the metal fine particle solution to at least one surface of the substrate, the humidity on the substrate is set to 1 to 1 at least from the start of application of the metal fine particle solution to the completion of application. It is preferable to control the atmosphere to satisfy the condition of 85% RH. The humidity on the substrate is preferably 10 to 70% RH, more preferably 20 to 60% RH, and particularly preferably 30 to 50% RH. That is, when the humidity on the substrate is less than 1%, the total light transmittance is lowered, and there may be a problem in terms of transparency of the network metal fine particle laminated substrate. Further, when the humidity on the substrate is higher than 85% RH, the structure connected in a mesh shape is removed, and therefore, in terms of conductivity when a transparent conductive substrate is formed using a mesh metal fine particle laminated substrate. Problems may arise.

  The humidity on the substrate is measured using a hygrometer as follows. That is, in the manufacturing process of laminating a network metal fine particle layer on a substrate, the humidity above 1 cm from the center of the surface of the substrate on which the metal fine particle solution is applied is measured using a hygrometer.

  In the present invention, when a metal fine particle solution that self-assembles into a mesh shape is used as the metal fine particle solution, the substrate as described above at least from the start of application of the metal fine particle solution until the metal fine particle solution becomes a mesh shape. It is preferable to maintain the above humidity at specific conditions.

  In the present invention, when the metal fine particle solution is applied to at least one surface of the substrate, the wind speed from all directions on the surface side of the substrate on which the metal fine particle solution is applied is at least from the start of the application of the metal fine particle solution to the completion of the application. It is preferable to control so as to satisfy the condition of 10 m / second or less. The wind speed is more preferably 5 m / sec or less, further preferably 1 m / sec or less, and particularly preferably 0.5 m / sec or less. That is, when the wind speed is higher than 10 m / second, the total light transmittance is lowered, and there may be a problem in terms of transparency of the network metal fine particle multilayer substrate. In addition, the structure connected in a mesh shape may be removed, which may cause a problem in conductivity when the mesh-like metal fine particle multilayer substrate is used as a transparent conductive substrate.

  The wind speed is measured using an anemometer as follows. That is, in the manufacturing process of laminating a mesh metal fine particle layer on a substrate, an anemometer is used, and the wind velocity from the lateral direction at a point at the center of the substrate is first 1 cm above the surface on which the metal fine particle solution is applied. The wind speed when the probe is placed horizontally with respect to the substrate is measured for 30 seconds in a stationary state (see FIG. 2). Subsequently, the wind speed when the probe placed horizontally is rotated 30 degrees, 60 degrees, 90 degrees, 120 degrees, 150 degrees, and 180 degrees about the probe longitudinal direction as an axis is measured for 30 seconds each ( (See FIG. 3). Next, the probe is rotated 45 degrees, 90 degrees, and 135 degrees clockwise around the axis perpendicular to the laminated substrate surface and passing through the center of the substrate from the first measured state. Measurement was performed (see FIG. 4). In this application, “the wind speed from all directions on the side of the substrate on which the metal fine particle solution is applied is 10 m / sec or less” means that the maximum wind speed is 10 m / sec or less at all points measured in this way. Means.

  In the present invention, the method of setting the wind speed from all directions on the side of the substrate on which the metal fine particle solution is applied to 10 m / sec or less is not particularly limited, but it is preferable to use an apparatus that surrounds the entire surface of the substrate with a shielding plate.

  In the present invention, when the metal fine particle solution is applied to at least one surface of the substrate, the temperature on the substrate is controlled to satisfy the condition of 5 to 100 ° C. at least from the start of the application of the metal fine particle solution to the completion of the application. It is preferable. The temperature on such a substrate is preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and particularly preferably 15 to 30 ° C. That is, when the temperature on the substrate is lower than 5 ° C. or higher than 100 ° C., the total light transmittance is lowered, which may cause a problem in terms of transparency of the network metal fine particle laminated substrate. In addition, the structure connected in a mesh shape may be removed, which may cause a problem in terms of conductivity when the mesh-like metal fine particle laminated substrate is used as a transparent conductive substrate.

  The temperature on the substrate is measured using a thermometer as follows. That is, in the manufacturing process of laminating the mesh metal fine particle layer on the substrate, the temperature 1 cm above the center of the surface on which the metal fine particle solution is applied is measured using a thermometer.

  The metal used for the metal fine particles in the present invention is not particularly limited, and examples thereof include platinum, gold, silver, copper, nickel, palladium, rhodium, ruthenium, bismuth, cobalt, iron, aluminum, zinc, and tin. A metal may be used by 1 type and may be used in combination of 2 or more type.

  The metal fine particle layer in the present invention is a layer composed of the metal fine particles as described above, and in addition to the metal fine particles, various other additives such as a dispersant, a surfactant, a protective resin, an antioxidant, It can contain an inorganic component such as a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a pigment, a dye, organic or inorganic fine particles, a filler, an antistatic agent, and an organic component.

  In the present invention, by increasing the conductivity of the metal fine particle layer by using a known method for increasing the conductivity of the metal fine particle layer, such as heat treatment, light treatment, energization treatment, etc. A transparent conductive substrate can be suitably obtained from the metal fine particle laminated substrate.

  In the present invention, if the heat treatment of the network metal fine particle laminated substrate for obtaining the transparent conductive substrate is performed at a high temperature of 200 ° C. or more for a long time, problems such as deformation of the substrate may occur, which is not preferable.

  Further, it is preferable to obtain a transparent conductive substrate by increasing the conductivity by a method of treating the metal fine particle layer of the network metal fine particle laminated substrate with an acid. Since the method of treating with an acid can increase the conductivity of the metal fine particles under mild processing conditions, if such mild processing conditions are selected, a material having poor heat resistance and light resistance, such as a thermoplastic resin, can be used as a substrate. Even when used as, it can be suitably acid-treated. In addition, this method is preferable in terms of productivity because it does not require complicated apparatuses or processes.

  Such an acid is not particularly limited, and can be selected from various organic acids and inorganic acids. Examples of the organic acid include acetic acid, oxalic acid, propionic acid, lactic acid, and benzenesulfonic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. These may be strong acids or weak acids. Preferred are acetic acid, hydrochloric acid, sulfuric acid, and aqueous solutions thereof, and more preferred are hydrochloric acid, sulfuric acid, and aqueous solutions thereof.

  A specific method of treating with such an acid is not particularly limited. For example, the substrate on which the metal fine particle layer is laminated in an acid or an acid solution is immersed, or an acid or an acid solution is immersed in the metal fine particle layer. For example, a method of applying to the top or applying a vapor of an acid or an acid solution to the silver fine particle layer is used.

  Further, it is preferable to treat the metal fine particle layer with an organic solvent before treating the metal fine particle layer of the network metal fine particle laminated substrate with an acid. As described above, when the metal fine particle layer of the network metal fine particle laminated substrate is treated with an organic solvent before the metal fine particle layer is treated with an acid, more excellent conductivity is easily obtained.

  As a step of treating such a metal fine particle layer with an organic solvent, a method of laminating metal fine particles in a network form on a substrate to form a network-like metal fine particle laminated substrate, and then treating with an organic solvent has an effect of increasing conductivity. Since it is excellent and efficient in terms of productivity, it is preferably used. In addition, before or after the treatment with the organic solvent, another layer may be printed on or applied to the substrate on which the metal fine particle layer is laminated. Further, before or after the treatment with the organic solvent, the substrate on which the metal fine particle layer is laminated may be dried, heat-treated, or subjected to an ultraviolet irradiation treatment.

  When the metal fine particle layer is treated with an organic solvent, the treatment temperature of the organic solvent is sufficient at room temperature. When the treatment is performed at a high temperature, when a thermoplastic resin film is used as the substrate, the substrate may be whitened and transparency may be impaired, which is not preferable. Such treatment temperature is preferably 40 ° C. or less, more preferably 30 ° C. or less, and particularly preferably 25 ° C. or less.

  The method for treating the metal fine particle layer with an organic solvent is not particularly limited. For example, the substrate on which the metal fine particle layer is laminated in a solution of the organic solvent, the organic solvent is applied on the metal fine particle layer, A method of applying a vapor of the solvent to the metal fine particle layer is used. Among these, a method of immersing a substrate in which a metal fine particle layer is laminated in an organic solvent or coating an organic solvent on the metal fine particle layer is preferable because of its excellent conductivity improving effect.

  Examples of such organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3 Alcohols such as butanediol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, esters such as ethyl acetate and butyl acetate, alkanes such as hexane, heptane, decane and cyclohexane, N- Dipolar aprotic solvents such as methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, toluene, xylene, aniline, ethylene glycol butyl ether, ethylene glycol, ethyl ether, ethylene glyco Methyl ether, chloroform, and may be used a mixture of these solvents. Among these, it is preferable that ketones, esters, and toluene are contained because the effect of improving conductivity is excellent, and ketones are particularly preferable.

  Regarding the conductivity of the transparent conductive substrate in the present invention, the surface specific resistance is preferably 30 Ω / □ or less. The surface specific resistance is more preferably 20Ω / □ or less, further preferably 10Ω / □ or less, and particularly preferably 4Ω / □ or less. When the surface specific resistance is 30 Ω / □ or less, a load due to resistance is reduced when the conductive substrate is energized, so that heat generation can be suppressed and the device can be used at a low voltage. Further, for example, when used as a transparent conductive substrate for an electromagnetic wave shielding substrate of a flat panel display such as a plasma display panel or a liquid crystal television, the electromagnetic wave shielding property is good, which is preferable.

  For the measurement of the surface specific resistance, for example, the reticulated metal fine particle laminated substrate is heat-treated at 150 ° C. for 2 minutes, placed in 1N hydrochloric acid, and left for 1 minute. Thereafter, the network-like fine metal particle multilayer substrate is taken out, washed with water, dried, left in a normal state (23 ° C., relative humidity 65%) for 24 hours, and in that atmosphere, in accordance with JIS-K-7194 (1994). And it can be measured using Loresta-EP (Mitsubishi Chemical Corporation make, model number: MCP-T360). If the surface specific resistance thus obtained is 30 Ω / □ or less, the conductivity is good.

  The substrate in the present invention is not particularly limited, and various substrates such as glass and resin can be used. In addition, a combination of two or more substrates such as glass and resin can be used.

  In the present invention, when the hydrophilic treatment layer is laminated on the surface of the substrate, it is preferable because the metal fine particles are easily laminated in a network shape. Such hydrophilic treatment layer is not particularly limited, but natural resins such as polyester, acrylic-modified polyester, polyurethane, acrylic resin, methacrylate resin, polyamide, polyvinyl alcohol, starches, cellulose derivatives, gelatin and the like. Polyvinyl pyrrolidone, polyvinyl butyral, polyacrylamide, epoxy resin, melamine resin, urea resin, polythiophene, polypyrrole, polyacetylene, polyaniline, various silicone resins and modified silicone resins can be used.

  In this invention, when a board | substrate is a thermoplastic resin film, it is preferable at points, such as being excellent in transparency, a softness | flexibility, and workability. The thermoplastic resin film as used in the present invention is a general term for films that are melted or softened by heat, and is not particularly limited, but representative examples include polyolefins such as polyester films, polypropylene films, and polyethylene films. Films, polylactic acid films, polycarbonate films, acrylic films such as polymethyl methacrylate films and polystyrene films, polyamide films such as nylon, polyvinyl chloride films, polyurethane films, fluorine films, polyphenylene sulfide films, and the like can be used.

  These thermoplastic resin films may be composed of homopolymers or copolymer polymers, but among these, in terms of mechanical properties, dimensional stability, transparency, polyester films, polypropylene films, Polyamide films are preferred, and polyester films are particularly preferred from the viewpoints of mechanical strength and versatility.

  In such a polyester film, polyester is a general term for polymers having an ester bond as a main bond chain, and includes ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2, It is preferable to use one having at least one component selected from 6-naphthalate, ethylene-α, β-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate as a main component. it can. These constituent components may be used alone or in combination of two or more. However, when quality, economy and the like are comprehensively judged, polyester having ethylene terephthalate as a main constituent, that is, polyethylene terephthalate is used. It is particularly preferable to use it. In addition, when heat or shrinkage stress acts on the substrate, polyethylene-2,6-naphthalate having excellent heat resistance and rigidity is more preferable. These polyesters may further be partially copolymerized with other dicarboxylic acid components and diol components, preferably 20 mol% or less.

  The intrinsic viscosity (measured in o-chlorophenol at 25 ° C.) of such polyester is preferably 0.4 to 1.2 dl / g, more preferably 0.5 to 0.8 dl / g. It is suitable for carrying out the invention.

  Further, in such a thermoplastic resin, for example, polyester, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye, organic or inorganic fine particles, Fillers, antistatic agents, nucleating agents and the like may be added to such an extent that the properties are not deteriorated.

  Such a thermoplastic resin film, such as a polyester film, is preferably biaxially oriented. Such a biaxially oriented polyester film is generally obtained by stretching an unstretched polyester sheet or film about 2.5 to 5 times in the longitudinal direction and in the width direction, and then performing heat treatment to complete the crystal orientation. Yes, it indicates a biaxially oriented pattern by wide-angle X-ray diffraction.

  The thickness of such a thermoplastic resin film, such as a polyester film, is not particularly limited and is appropriately selected depending on the application and type, but from the viewpoint of mechanical strength, handling properties, etc., preferably 10 to 500 μm, More preferably, it is 38-250 micrometers, Most preferably, it is 75-150 micrometers. For example, when a polyester film is used as the substrate, a composite film by coextrusion may be used. On the other hand, a film obtained by bonding the obtained film by various methods can also be used.

  In addition to the substrate and the metal fine particle layer, various layers may be laminated on the network metal fine particle laminated substrate of the present invention. For example, although not particularly limited, an undercoat layer for improving adhesion may be provided between the substrate and the metal fine particle layer, or a protective layer may be provided on the metal fine particle layer. In addition, an adhesive layer, a release layer, a protective layer, an adhesion-imparting layer, a weather-resistant layer, or the like may be provided on one side or both sides of the substrate. In addition, when various layers are formed on the substrate surface on the side not having the metal fine particle layer, various layers can be formed without any particular limitation, but when various layers are provided between the substrate and the metal fine particle layer Note the following points. That is, when such various layers are provided between the substrate and the metal fine particle layer, it is important that the surface wetting tension of the various layers on the substrate to which the metal fine particle solution is applied is 45 mN / m or more and 73 mN / m or less. As long as these layers have the surface wetting tension described above, various layers can be provided on the substrate in the present invention.

  Hereinafter, although the manufacturing method of the network metal fine particle laminated substrate of this invention is illustrated and demonstrated more concretely, this invention is not limited to this. That is, a hydrophilic treatment layer is laminated on a biaxially stretched polyester film having a surface wetting tension of 47 mN / m, a silver fine particle solution is applied by a die coating method that does not come into contact with the substrate, and the silver fine particle layer is laminated in a mesh shape. By using the method for producing a reticulated metal fine particle multilayer substrate of the present invention, a reticulated metal fine particle multilayer substrate having excellent transparency and moire resistance and having no scratches or streaks on the coating film is obtained by a method having excellent productivity. be able to. Since the biaxially stretched polyester film described here has a surface wetting tension of 47 mN / m, a relatively excellent network metal fine particle multilayer substrate can be obtained without providing a hydrophilic treatment layer.

  Further, in order to obtain a transparent conductive substrate from the thus obtained mesh-like metal fine particle laminated substrate, for example, the mesh-like metal fine particle laminated substrate is heat-treated at 150 ° C. for 2 minutes and treated with acetone for 30 seconds. Put in 1N hydrochloric acid and let stand for 1 minute. Thereafter, the network-like fine metal particle multilayer substrate is taken out, washed with water, and dried to be suitably obtained.

The transparent conductive substrate using the reticulated metal fine particle multilayer substrate of the present invention has transparency and a high level of conductivity, and therefore, an electromagnetic wave shielding film used for flat panel displays such as plasma display panels and liquid crystal televisions. In addition, it can be suitably used for various conductive substrate applications such as circuit material applications and solar cell applications.
[Characteristic measurement method and effect evaluation method]
The method for measuring the characteristics of the conductive substrates prepared in each of the examples and comparative examples and the method for evaluating the effects are as follows.

(1) Surface Wetting Tension The surface wetting tension of the substrate was measured according to JIS- in the atmosphere after leaving the substrate used in each Example / Comparative Example in a normal state (23 ° C., relative humidity 50%) for 6 hours. It carried out in the form based on K-6768 (1999).

  First, the surface to be measured of the substrate is placed on the base of the hand coater, a few drops of the surface wetting tension test liquid mixture are dropped, and a wire bar capable of applying a WET thickness of 12 μm is immediately drawn and spread.

  The surface wetting tension is judged by observing the liquid film of the test mixed solution in a bright place and in the state of the liquid film after 2 seconds. If the liquid film is not torn and remains in the applied state for 2 seconds or longer, it is wet. When the wetting is maintained for 2 seconds or more, the process further proceeds to a liquid mixture with a high surface wetting tension. Conversely, when the liquid film is broken in less than 2 seconds, the process proceeds to a liquid mixture with a low surface wetting tension. This operation is repeated, and a liquid mixture that can wet the surface of the substrate accurately for 2 seconds or more is selected to obtain the surface wet tension of the substrate. The maximum surface wetting tension by this measurement method is 73 mN / m.

  The unit of surface wetting tension is mN / m.

(2) Surface observation (shape observation)
The surface of the reticulated metal fine particle multilayer substrate was observed with a differential interference microscope (LEICA DMLM manufactured by Leica Microsystems Co., Ltd.) at a magnification of 100 to observe the shape of the reticulated mesh.

(3) Surface specific resistance The surface specific resistance is measured by subjecting the metal fine particle laminated substrate obtained in each of the examples and comparative examples to heat treatment at 150 ° C. for 2 minutes, and in 1N hydrochloric acid for 1 minute. Thereafter, the metal fine particle multilayer substrate is taken out, washed with water, dried, left in a normal state (23 ° C., relative humidity 65%) for 24 hours, and then in that atmosphere, in accordance with JIS-K-7194 (1994). Then, it implemented using Loresta-EP (Mitsubishi Chemical Corporation make, model number: MCP-T360). The unit is Ω / □.

In addition, this measuring device can measure below 1 × 10 ⁶ Ω / □. If the surface specific resistance is 30Ω / □ or less, the conductivity is good.

(4) Total light transmittance The total light transmittance is as follows. Fully automatic direct reading haze computer manufactured by Suga Test Instruments Co., Ltd. It measured using "HGM-2DP". The average value measured three times was taken as the total light transmittance of the network metal fine particle laminated substrate.

  If the total light transmittance is 50% or more, the transparency is good. In addition, in the case of the laminated substrate which laminated | stacked the metal fine particle layer only on the single side | surface of the board | substrate, the board | substrate was installed so that light may enter from the surface side which laminated | stacked the metal fine particle layer.

(5) Humidity on the substrate when forming the metal fine particle layer In the manufacturing process of laminating the mesh metal fine particle layer on the substrate, the humidity is 1 cm above the laminated substrate to CLIMOMASTER (made by MODEL 6531 Nippon Kanomax Co., Ltd.). Measured. Humidity was measured for 15 seconds or more above 1 cm from the center of the surface of the substrate on which the metal fine particle solution was applied, and was taken as a stable value.

(6) Temperature on the substrate when forming the metal fine particle layer The temperature is set to CLIMOMASTER (MODEL 6531 made by Nippon Kanomax Co., Ltd.) 1 cm above the laminated substrate in the production process of laminating the network metal fine particle layer on the substrate. Measured. The temperature was measured at 1 cm above the center of the surface of the substrate on which the metal fine particle solution was applied for 30 seconds or more, and was taken as a stable value.

(7) Wind speed on the substrate when forming the metal fine particle layer In the manufacturing process of laminating the mesh metal fine particle layer on the substrate, the wind speed is set to CLIMOMASTER (MODEL 6531 made by Nippon Kanomax Co., Ltd.) 1 cm above the laminated substrate. Measured. The measurement was performed in the order of (i) to (iii) below.
(I) When the probe is placed horizontally with the substrate so as to receive the wind velocity from the lateral direction at one point at the center of the substrate, as shown in FIG. The wind speed was measured for 30 seconds in a stationary state.
(Ii) As shown in FIG. 3, the wind speed when the probe placed horizontally is rotated by 30 degrees, 60 degrees, 90 degrees, 120 degrees, 150 degrees, and 180 degrees about the longitudinal direction of the probe is stationary. The state was measured for 30 seconds.
(Iii) From the state measured in (i), as shown in FIG. 4, the probe is rotated clockwise by 45 degrees, 90 degrees, and 135 degrees about the axis perpendicular to the substrate surface and passing through the center of the substrate. ), The wind speed when the probe placed horizontally was rotated 0, 30, 60, 120, 150, and 180 degrees was measured for 30 seconds in a stationary state.

  The wind speed was set to the maximum value among the wind speeds measured at each point as described above.

(8) Moire resistance The anti-moire phenomenon is caused by using a VIERA TH-42PX50 manufactured by Matsushita Electric Industrial Co., Ltd. as a plasma display on which an image is projected. The substrate was held so as to be parallel, and the substrate was rotated 360 ° while the screen and the surface of the substrate were kept substantially parallel, and it was evaluated by visually observing whether the moire phenomenon occurred during the rotation.

  The case where no moiré was observed was indicated by “◯”, and the case where moiré was observed was indicated by “x”. A case where moiré was partially observed was indicated as “Δ”. If the visual observation was “◯”, the moire phenomenon was considered good.

  In addition, when the metal fine particle layer was laminated | stacked only on the single side | surface of the board | substrate, it had the mesh-like metal fine particle laminated board so that the surface side which has not laminated | stacked the metal fine particle layer may oppose a display screen.

  Next, the present invention will be described based on examples.

(Metal fine particle solution 1)
As the metal fine particle solution 1, CE103-7 manufactured by Cima NanoTech, which is a silver fine particle solution, was used.

(Coating liquid A)
As the coating liquid A, a 3.0 wt% solution of acrylamide (polymer, MW (weight average molecular weight) 600000 to 1000000, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(Coating fluid B)
As the coating solution B, a water-dispersed acrylic copolymer resin water ratio 3.0 wt% solution was used.
Example 1
Biaxially stretched polyethylene terephthalate film in a hot air oven (PHH-200 manufactured by Tabay Espec Co., Ltd.) with humidity of 30% RH, temperature of 25 ° C., and an air flow scale adjusted and maintained at an air velocity of 0.6 m / sec. The metal fine particle solution 1 was applied to Lumirror (registered trademark) U46 manufactured by Toray Industries, Inc., surface wetting tension 47 mN / m) using an applicator method not contacting the substrate so as to have a WET thickness of 30 μm.

  Next, the coated laminated substrate was allowed to pass for 10 minutes at room temperature to obtain a laminated substrate (network metal fine particle laminated substrate) on which silver fine particle layers were laminated. At 72%, the moire resistance was also good and “◯”.

  Next, this laminated substrate was heat-treated for 2 minutes in a hot air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) at 150 ° C. Subsequently, the laminated substrate was immersed in acetone (manufactured by Sasaki Chemical Co., Ltd.) at 25 ° C. for 30 seconds (acetone treatment), and the laminated substrate was taken out and dried at 25 ° C. for 3 minutes. Next, in order to acid-treat the silver particle layer of this laminated substrate, it was immersed in 1N hydrochloric acid (1N hydrochloric acid manufactured by Nacalai Tesque Co., Ltd.) for 1 minute. Thereafter, the multilayer substrate was taken out, washed with water, and then dried for 2 minutes in a hot air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) at 150 ° C. in order to remove moisture.

The surface specific resistance of this laminated substrate (transparent conductive substrate) was 20Ω / □.
(Example 2)
A primer was applied to one side of a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) U46 manufactured by Toray Industries, Inc., surface wetting tension 47 mN / m), and hydrophilic treatment was performed. The surface wetting tension of the substrate subjected to the hydrophilic treatment was 73 mN / m. Subsequently, the inside of a hot air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) was adjusted to a humidity of 30% RH, a temperature of 25 ° C., and the air volume scale was adjusted to maintain an air velocity of 0.6 m / sec. In this hot air oven, the metal fine particle solution 1 was applied on the hydrophilic treatment layer of the biaxially stretched polyethylene terephthalate film by using a die coating method so as to have a WET thickness of 30 μm and not in contact with the substrate.

  Next, the coated laminated substrate was allowed to pass for 10 minutes at room temperature to obtain a laminated substrate (network metal fine particle laminated substrate) on which silver fine particle layers were laminated.

  This laminated substrate had a mesh shape, had a total light transmittance of 80%, good moiré resistance, and “◯”.

  Next, similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 3Ω / □.

(Example 3)
A laminated substrate (network metal fine particle laminated substrate) was prepared in the same manner as in Example 2 except that the metal fine particle solution 1 was applied using an applicator method that did not contact the substrate.

  This laminated substrate had a mesh shape, had a total light transmittance of 80%, good moiré resistance, and “◯”.

  Next, similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 5Ω / □.

Example 4
A laminated substrate (network metal fine particle laminated substrate) was prepared in the same manner as in Example 2 except that the metal fine particle solution 1 was applied by using a comma coating method without contacting the substrate.

  This laminated substrate had a mesh shape, had a total light transmittance of 80%, good moiré resistance, and “◯”.

  Next, similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 8Ω / □.

(Example 5)
Coating liquid A was applied to one side of a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) T60, manufactured by Toray Industries, Inc.) with a wire bar so that the wet thickness was 12 μm, and a hot air oven at 120 ° C. (Tabaie Speck Co., Ltd.) Manufactured by PHH-200) for 1 minute to laminate a hydrophilic treatment layer. The surface wetting tension of the surface coated with the hydrophilic treatment layer was measured and found to be 60 mN / m. Next, the inside of a hot-air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) was maintained in an atmosphere with a humidity of 30% RH, a temperature of 25 ° C., and an air volume scale adjusted to a wind speed of 0.6 m / sec. In this hot air oven, the metal fine particle solution 1 was applied on the hydrophilic treatment layer of the biaxially stretched polyethylene terephthalate film using an applicator method that does not contact the substrate so as to have a WET thickness of 30 μm.

  Next, the coated laminated substrate was allowed to pass for 10 minutes at room temperature to obtain a laminated substrate (network metal fine particle laminated substrate) on which silver fine particle layers were laminated.

  This laminated substrate was network-like, had a total light transmittance of 58%, good moiré resistance, and “◯”.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 30Ω / □.

(Example 6)
On one side of a biaxially stretched polyethylene terephthalate film (Lumilar (registered trademark) T60, manufactured by Toray Industries, Inc.), a mixed coating solution in which coating solution A / coating solution B = 75/25 by weight ratio is set to a WET thickness of 12 μm. It apply | coated with the wire bar, it dried for 1 minute with 120 degreeC hot-air oven (Tabei ESPEC Co., Ltd. PHH-200), and the hydrophilic treatment layer was laminated | stacked. The surface wetting tension of the surface coated with the hydrophilic treatment layer was measured and found to be 73 mN / m. Next, the inside of a hot-air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) was maintained in an atmosphere with a humidity of 30% RH, a temperature of 25 ° C., and an air volume scale adjusted to a wind speed of 0.6 m / sec. In this hot air oven, the metal fine particle solution 1 was applied on the hydrophilic treatment layer of the biaxially stretched polyethylene terephthalate film using an applicator method that does not contact the substrate so as to have a WET thickness of 30 μm.

  Next, the coated laminated substrate was allowed to pass for 10 minutes at room temperature to obtain a laminated substrate (network metal fine particle laminated substrate) on which silver fine particle layers were laminated.

  This laminated substrate had a mesh shape, had a total light transmittance of 62%, good moiré resistance, and “◯”.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 20Ω / □.

(Example 7)
Coating liquid A was applied to one side of a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) T60, manufactured by Toray Industries, Inc.) with a wire bar so that the wet thickness was 12 μm, and a hot air oven at 120 ° C. (Tabaie Speck Co., Ltd.) Manufactured by PHH-200) for 1 minute to laminate a hydrophilic treatment layer. Then, the primer was apply | coated to the surface which apply | coated the coating liquid A, and also the hydrophilic process was performed. The surface wetting tension of the substrate subjected to the hydrophilic treatment was 73 mN / m. Next, the inside of a hot-air oven (PHH-200 manufactured by Tabai Espec Co., Ltd.) was maintained in an atmosphere with a humidity of 30% RH, a temperature of 25 ° C., and an air volume scale adjusted to a wind speed of 0.6 m / sec. In this hot air oven, the metal fine particle solution 1 was applied on the hydrophilic treatment layer of the biaxially stretched polyethylene terephthalate film using an applicator method that does not contact the substrate so as to have a WET thickness of 30 μm.

  Next, the coated laminated substrate was allowed to pass for 10 minutes at room temperature to obtain a laminated substrate (network metal fine particle laminated substrate) on which silver fine particle layers were laminated.

  This laminated substrate had a mesh shape, had a total light transmittance of 80%, good moiré resistance, and “◯”.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface specific resistance of this laminated substrate (transparent conductive substrate) was 12Ω / □.

(Comparative Example 1)
A laminated substrate was prepared in the same manner as in Example 1 except that the metal fine particle solution 1 was applied to a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) U34 manufactured by Toray Industries, Inc., surface wetting tension 37 mN / m).

  This laminated substrate did not have a mesh shape, and the total light transmittance was as low as 45%.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface resistivity of this multilayer substrate was 300Ω / □.

(Comparative Example 2)
A laminated substrate was prepared in the same manner as in Example 1 except that the metal fine particle solution 1 was applied to a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) U426 manufactured by Toray Industries, Inc., surface wetting tension 44 mN / m).

  This laminated substrate did not have a mesh shape, and the total light transmittance was as low as 43%.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface resistivity of this multilayer substrate was 500Ω / □.

(Comparative Example 3)
A laminated substrate was prepared in the same manner as in Example 1 except that the metal fine particle solution 1 was applied to a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc., surface wetting tension 39 mN / m).

  This laminated substrate did not have a mesh shape, and the total light transmittance was as low as 47%.

  Similarly to Example 1, the obtained laminated substrate was subjected to heat treatment, acetone treatment, acid treatment, water washing, and drying in this order.

  The surface resistivity of this multilayer substrate was 500Ω / □.

(Comparative Example 4)
A laminated substrate (network metal fine particle laminated substrate) was prepared in the same manner as in Example 2 except that the metal fine particle solution 1 was applied using a wire bar in contact with the substrate.

  Although the total light transmittance of this laminated substrate was 80%, the laminated network metal fine particle laminated substrate had a mesh-like structure in the portion where the laminated substrate was not in contact with the portion in contact with the wire bar along the wire pitch of the wire bar. The size of the parts is different, the gaps in the parts that are in contact are large, and the parts that are not in contact are alternately arranged with different large and small gaps in which the gaps are small, resulting in streak-like defects, a regular pattern, and lamination When the network-like fine metal particle multilayer substrate was used while being bonded to a plasma display, a moire phenomenon partially occurred, which was evaluated as “Δ”.

  Next, in the same manner as in Example 1, the obtained multilayer substrate was subjected to heat treatment, acid treatment, water washing, and drying in this order to obtain a multilayer substrate (transparent conductive substrate) having a surface specific resistance of 4Ω / □.

(Comparative Example 5)
A laminated substrate was prepared in the same manner as in Example 2 except that the fine metal particle solution 1 was applied using a gravure coater that contacted the substrate.

  Although the total light transmittance of this laminated substrate was 70%, the hydrophilic treatment layer in contact with the substrate was scraped off to form a gravure plate without becoming a network.

Next, similarly to Example 1, the obtained multilayer substrate was subjected to heat treatment, acid treatment, water washing, and drying in this order to obtain a multilayer substrate (transparent conductive substrate) having a surface specific resistance of 10Ω / □.
Table 1 shows the evaluation of Examples 1, 2, 3, 4, 5, and 6 and Comparative Examples 1, 2, 3, 4, and 5.

  According to the method for producing a reticulated metal fine particle multilayer substrate of the present invention, a reticulated metal fine particle multilayer substrate having excellent transparency and moire resistance, and eliminating defects such as streaks and scratches on the coating film is excellent in productivity. Can be obtained by different methods.

  The transparent conductive substrate using the network-like fine metal particle multilayer substrate of the present invention has transparency and a high level of conductivity, and also has excellent moire resistance. For example, a flat plate such as a plasma display panel or a liquid crystal television is used. It can be suitably used for a panel display.

It is a top view which shows an example of the network structure in the network metal fine particle laminated substrate of this invention. It is the schematic shown typically explaining the method to measure the wind speed on a board | substrate. FIG. 3 is a side view for explaining that the probe is rotated about the longitudinal direction as an axis in the wind speed measuring method in FIG. 2 (a view when FIG. 2 is viewed from the A direction). FIG. 3 is a plan view for explaining that the probe is rotated about an axis perpendicular to the laminated substrate in the wind speed measuring method in FIG. 2 (a view when FIG. 2 is viewed from the B direction).

Explanation of symbols

1 Laminated substrate 2 Probe 3 Measuring hole 4 Wind speed measuring device

Claims (7)

  A metal fine particle layer is formed on a substrate by applying a metal fine particle solution to a surface having a surface wet tension of 45 mN / m or more and 73 mN / m or less and a surface wet tension of 45 mN / m or more and 73 mN / m or less on at least one side of the substrate. A method for producing a mesh metal fine particle laminate substrate, wherein the metal fine particle solution is laminated by a non-contact coating method that does not contact the substrate. .   The method for producing a reticulated metal fine particle laminated substrate according to claim 1, wherein the metal fine particle solution is a metal fine particle solution that self-assembles into a mesh shape.   The method for producing a reticulated metal fine particle laminated substrate according to claim 1 or 2, wherein the substrate is a thermoplastic resin film.   A metal fine particle layer of a network metal fine particle laminated substrate produced by the method according to any one of claims 1 to 3, wherein the metal fine particle layer is treated with an organic solvent and then treated with an acid. Production method.   A network-like fine metal particle multilayer substrate obtainable by the production method according to claim 1.   A transparent conductive substrate obtainable by the production method according to claim 4.   The transparent conductive substrate according to claim 6, wherein the transparent conductive substrate is used as an electromagnetic wave shielding substrate of a plasma display panel.

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