JP2020203410A - Method for producing transparent conductive base material in which graphene joined body composed of aggregate of graphene obtained by joining overlapping flat surfaces of graphene is thermocompression-bonded to transparent film of synthetic resin - Google Patents

Abstract

To firstly produce an assembly of graphene in a container filled with a liquid, secondary arrange a transparent base material in a bottom surface of the container, overlap flat surfaces of the graphene each other through a liquid thereon, and thirdly thermocompression-bonding a graphene joined body obtained by uniformly compressing the assembly of the graphene and joining the flat surfaces while overlapping each other to the transparent base material.SOLUTION: The first step produces an assembly of graphene from graphite particles in methanol. The second step arranges a transparent film on a bottom surface of a container, and makes flat surfaces of the graphene overlap each other through the ethanol thereon. The third step uniformly compresses the plane of the aggregate of the graphene, and raises the temperature of the container to Vicat softening temperature of the synthetic resin. Thereby, in the graphene joined body whose flat surfaces are joined to each other, the transparent conductive base material performs thermo-compression to the transparent film is formed as the shape of the bottom surface on the bottom surface of the container.SELECTED DRAWING: Figure 1

Description

The present invention is a method for producing a transparent conductive base material in which a graphene joint composed of a collection of graphene obtained by joining the flat surfaces of graphene on which the flat surfaces of graphene are overlapped is thermocompression bonded to a transparent film of a synthetic resin. Get involved. That is, the graphene joint having the property of transparent conductivity is extremely thin and difficult to handle. However, by thermocompression bonding the graphene bonded body to a transparent film made of synthetic resin, a transparent conductive base material that is easy to handle can be obtained.
That is, graphene is a single crystal material composed of a collection of carbon atoms that two-dimensionally forms a network structure in which carbon atoms are hexagonal. Therefore, the thickness is 0.332 nm, which is three orders of magnitude smaller than the wavelength of visible light, and therefore has transparency through which visible light is transmitted. The thermal conductivity is 19.5 W / Cm, which is 4.5 times the thermal conductivity of silver, which has the highest thermal conductivity among metals. Furthermore, the electrical conductivity is 7.5 × ¹⁰ 7 S / m, with a 1.2-fold electrical conductivity of silver electrical conductivity. Therefore, the graphene bonded body obtained by superimposing and joining the flat surfaces of graphene is a transparent conductive film having a certain area and having transparency, thermal conductivity, and electrical conductivity similar to those of graphene.
Therefore, the transparent conductive base material obtained by thermocompression-bonding a graphene junction having excellent transparency, thermal conductivity, and electrical conductivity to a transparent film of synthetic resin has a certain thickness and is easy to handle. Become. Thereby, this transparent conductive base material can be widely applied to a transparent conductive base material for a touch panel, a flexible circuit board, a transparent conductive base material of an organic EL, a transparent conductive base material of an organic thin-film solar cell, a flexible LED conductive film, and the like.

Conventional methods for producing a transparent conductive film include a method of applying a conductive ink or a conductive paste to a transparent substrate and a method of forming a transparent conductive film on the transparent substrate by physical vapor deposition or chemical vapor deposition.
For example, in Patent Document 1, a conductive paste made of a binder resin and conductive oxide fine particles made of tin oxide, antimony-doped tin oxide or phosphorus-doped tin oxide is applied or printed on a substrate to form a transparent conductive film. The technology to be used is described.
Further, Patent Document 2 describes a technique for forming a transparent conductive thin film in which a metal oxide layer, a silicon oxide layer and an indium tin oxide layer are laminated on a transparent plastic base material by magnetron sputtering.

However, the conventional method of forming a transparent conductive film on a transparent substrate has the problems described below.
First, the problem of forming a transparent conductive film by applying a conductive ink or a conductive paste will be described. In each of the conductive ink or the conductive paste, metal fine particles, metal powder or conductive metal oxide fine particles are dispersed as a conductive filler in a vehicle composed of a binder of a synthetic resin and a solvent. Therefore, there is a problem caused by using the conductive filler and a problem caused by dispersing the conductive filler in the vehicle.
The first problem is due to the use of conductive fillers. That is, the coated or printed ink or paste is heat-treated to cure the resin, and the cured resin binds the conductive filler to form a transparent conductive film. However, the cured resin prevents the conductive fillers from being directly bonded to each other, and the electrical resistance of the transparent conductive film increases. Therefore, when an electric current is passed through the transparent conductive film, heat is generated, and deterioration and peeling of the transparent conductive film are promoted.
The second problem is due to the dispersibility of the conductive filler. That is, if the dispersibility of the conductive filler in the vehicle is poor, the conductive filler is unevenly distributed after the heat treatment. As a result, the electrical resistance of the transparent conductive film increases as described above. On the other hand, if the amount of the organic compound adsorbed on the conductive filler is increased in order to increase the dispersibility of the conductive filler, the electrical resistance of the transparent conductive film after the heat treatment increases because the organic compound is an insulator.
The third problem is due to the aggregation of the conductive fillers. The finer the conductive filler, the easier it is to aggregate, and once the fillers aggregate, the aggregation cannot be released. As a result, the dispersibility of the filler in the vehicle deteriorates, and the electrical resistance of the transparent conductive film increases.
The above-mentioned problems are fundamental problems caused by using a conductive filler and dispersing the conductive filler, and are difficult to solve. Therefore, there is a strong demand for a technique for forming a transparent conductive film by a method other than using a conductive ink or a conductive paste.

Next, the problem of forming a transparent conductive film by physical vapor deposition or chemical vapor deposition will be described. Here, the problems will be described focusing on the most commonly used sputtering method, but the formation of a transparent conductive film by chemical vapor deposition also has a similar problem.
First, the principle of forming a transparent conductive film by the sputtering method is that ions collide with the target at high speed to knock out the atoms that make up the target, and the knocked out atoms plunge into the transparent substrate and the atoms are deposited. To form a transparent conductive film. Since the atoms knocked out from the target travel straight toward the transparent substrate, defects such as protrusions called nodules are likely to occur depending on the surface condition of the transparent substrate. Therefore, it is necessary to correct structural defects by annealing treatment. This annealing treatment increases the cost of forming the transparent conductive film.
Second, when atoms are ejected from the target, rebound particles are generated on the target, and when the rebound particles rush into the transparent substrate, the transparent conductive film is damaged. Therefore, a magnetron sputtering device is used to lower the magnetron impedance to lower the discharge voltage and alleviate the damage caused by the recoil particles. However, it is necessary to raise the temperature of the transparent substrate and leave it for a long time, and the transparent conductive film is formed on the transparent film of an inexpensive synthetic resin film which is inferior in heat resistance or dimensional stability when the temperature is raised. It becomes difficult.
Third, the vacuum chamber is evacuated once, and then sputtering is performed. During evacuation, moisture and foreign matter are gasified from the transparent substrate and released into the atmosphere of the transparent conductive film, which hinders the formation of a low-resistance transparent conductive film. Therefore, it is necessary to evacuate the transparent base material sufficiently in advance and vacuum-clean the surface of the transparent base material. This vacuum cleaning increases the cost of forming the transparent conductive film.
Fourth, when the electrode pattern is formed on the transparent substrate, the transparent conductive film is patterned by etching after forming the transparent conductive film. Therefore, the transparent base material and the transparent conductive film need to have chemical resistance to the etching solution. Also, the cost of forming the electrode pattern increases with the etching process.
Fifth, since the transparent conductive film formed by the sputtering method does not have sufficient conductivity, an annealing treatment accompanied by heat treatment is required. Therefore, the transparent conductive film once formed is left for a long time in an atmosphere where oxygen gas does not exist to perform the annealing treatment. This annealing treatment limits the material of the transparent substrate.
Sixth, in the sputtering method, the resistivity of the transparent conductive film increases as the distance from the center of the target increases by a certain distance. Therefore, it is not suitable for producing a transparent conductive film having a large area.
Since all of the above problems depend on the principle of forming a transparent conductive film by the sputtering method, it is difficult to solve them. Therefore, there is a strong demand for a technique for forming a transparent conductive film by a method other than the sputtering method.

On the other hand, graphene is produced by various methods, but when it is used as a transparent conductive film, a certain area is required, and the larger the area of graphene, the higher the production cost.
For example, Patent Document 3 describes a method for producing graphene by thermally decomposing a single crystal of silicon carbide. That is, the silicon carbide is heated in an inert atmosphere to thermally decompose the surface. At this time, silicon having a relatively low sublimation temperature is preferentially sublimated, and graphene is produced by the remaining carbon. However, a single crystal of silicon carbide is a very expensive material, and the larger the area, the more costly it is to grow the single crystal. Further, silicon is sublimated at a high temperature exceeding 1600 ° C. and in an atmosphere with a high degree of vacuum, but if even a small amount of silicon remains or impurities other than carbon are present, graphene is used as a residue after thermal decomposition. Not generated. Therefore, the cost of producing a single crystal of carbonized silica and the thermal decomposition treatment of the single crystal becomes expensive.
Further, Patent Document 4 describes a method for producing graphene by bringing a carbon-based substance into contact with a sheet-shaped single crystal graphitized metal catalyst and heat-treating it in a reducing atmosphere. First, the production cost of producing a single crystal graphitized metal catalyst is higher than that of a silicon carbide single crystal, and the larger the area, the higher the production cost of the single crystal. Second, when a single crystal graphitized metal catalyst is brought into contact with a carbon-based substance, if impurities other than carbon remain or are produced, graphene is not produced. Thirdly, the method of reducing the graphitized metal catalyst in an atmosphere rich in nitrogen gas containing hydrogen gas at a high temperature exceeding 1000 ° C. increases the heat treatment cost.

The graphene production method to date is not an inexpensive production method. Further, graphene used as a transparent conductive film needs to have a certain area. However, the larger the area, the higher the production cost of graphene, and the more it cannot be used as a general-purpose transparent conductive film. Second, the graphene produced is not necessarily graphene. That is, graphene is a single crystal material composed of a collection of carbon atoms that two-dimensionally forms a network structure in which carbon atoms are hexagonal, and in an atmosphere where no impurities are generated or in an environment where no impurities are generated. If crystal growth of only carbon atoms is not possible, graphene will not be produced. Further, since the graphene produced is extremely thin and extremely lightweight, it is troublesome to confirm that the produced product is graphene.
Therefore, the present inventor has found a method in which all the graphene produced is complete graphene and a large amount of graphene is instantly produced by an extremely simple method (Patent Document 5). That is, it is a technique for instantly producing a large amount of graphene from graphite particles, which is the cheapest carbon material, which is composed of only a single crystal of graphite, and the crystallization of graphite proceeds 100%. That is, a mass of natural graphite crystals is crushed, and a collection of graphite particles obtained by selecting scaly graphite particles or lumpy graphite particles from the crushed graphite crystals is pulled into the gap between two parallel plate electrodes, and the two sheets are pulled. This is a method in which an electric field is applied to the parallel plate electrodes of the above, and the interlayer bond of the basal plane of all graphite crystals forming graphite particles is simultaneously destroyed by the application of the electric field, and a large amount of graphene composed of the basal plane is produced. According to this method, a collection of 1.62 × 10 ¹³ graphene particles can be instantly obtained from only 1 g of scaly graphite particles or lump graphite particles.
However, the area of graphene produced from graphite particles is too small to be used as a transparent conductive film. Therefore, if the flat surfaces of graphene can be bonded to each other by an inexpensive method, a graphene bonded body having a large area can be used as an inexpensive transparent conductive film. Further, since the graphene joint is thin, if it can be integrated with a transparent base material made of another material, the graphene joint can be easily handled. Therefore, there is a demand for a technique for joining the flat surfaces of graphene and a technique for integrating the graphene joint with a transparent base material made of another material.

JP-A-2015-220192 Japanese Unexamined Patent Publication No. 2011-006937 JP-A-2015-110485 JP-A-2009-143799 Patent No. 6166860

Nir RR, et al. , Science 320, 1308 (2008)

Although a large amount of graphene can be instantly produced by the method according to Patent Document 5, a method for producing a graphene conjugate in which flat planes of graphene are bonded to each other using this group of graphene has not yet been found. Graphene is an extremely thin substance composed of a single crystallite, which two-dimensionally forms a network structure in which carbon atoms are hexagonal, is extremely lightweight, and has almost no mass. Therefore, in the method for producing an aggregate of graphene in Patent Document 5, when a large amount of graphene is precipitated, the graphene is scattered. In addition, graphene is easily scattered when handling the produced graphene. As described above, graphene is a difficult material to handle.
On the other hand, regarding the transparency of graphene, according to Non-Patent Document 1, the transmittance of visible light is 97.7%, and the absorbance per layer of graphene is 2.3%. For this reason, the transparency of a graphene conjugate obtained by joining the flat surfaces of graphene decreases as the number of bonded graphenes increases. On the other hand, tin oxide-doped indium oxide (In ₂ O _3- SnO ₂ , commonly known as ITO) is currently the most widely used transparent conductive film, and the transmittance of visible light of ITO is 84%. Therefore, in order to obtain transparency superior to that of ITO, it is necessary to keep the number of graphene bonded to 7 or less in the graphene bonded body. However, the thickness of the graphene joint body in which the number of graphene joints is suppressed to 7 or less is as thin as 2.3 nm or less, and it is transparent, so that it is difficult to handle. Therefore, if the transparent conductive graphene joint can be integrated with the transparent base material made of another material, the graphene joint becomes a transparent conductive base material that is easy to handle.
Therefore, in order to use graphene as a general-purpose transparent conductive base material, the following five problems can be raised as problems to be solved.
First, a collection of graphene is produced in a container filled with liquid. As a result, the graphene precipitated in the liquid does not scatter during and after the production of graphene.
Secondly, the flat surfaces of graphene are superposed on the bottom surface of the container via the liquid described above. After that, when the liquid is vaporized, a collection of graphene in which the flat surfaces are overlapped is formed on the bottom surface of the container. This prepares the graphene conjugate to form in the vessel. That is, the thickness of graphene is extremely thin, and the aspect ratio, which is the ratio of the surface area to the thickness, is extremely large. In addition, graphene is extremely thin and has almost no mass. Therefore, a group of graphene in which flat surfaces overlap each other can be formed on the bottom surface of the container by a method utilizing these two characteristics.
Thirdly, the portions where the flat surfaces of graphene overlap each other are joined, and a graphene bonded body in which the flat surfaces overlap and join is formed on the bottom surface of the container as the shape of the bottom surface. That is, graphene has a breaking strength of 42 N / m, which is a tough material having a strength more than 100 times that of steel. Therefore, by a method utilizing this feature, the portions where the flat surfaces overlap can be joined. As a result, the area limitation and the shape limitation of the graphene joint are removed, and the graphene joint can be used as the transparent conductive base material.
Fourth, the graphene junction described above is integrated with a transparent base material made of another material. That is, in order to obtain transparency superior to that of ITO, it is necessary to limit the number of graphene flat surfaces bonded to each other to 7 or less. However, the thickness of the graphene junction is as thin as 2.3 nm or less, and it is not easy to handle. Therefore, if the transparent conductive graphene joint can be integrated with the transparent base material made of another material, the graphene joint can be easily handled, and the graphene joint can be used as a general-purpose transparent conductive base material. it can.
Fifth, the treatments in the above four steps are all extremely simple, and the material used is an inexpensive material. As a result, using an inexpensive graphite particle aggregate, a graphene aggregate is produced by an inexpensive method, a graphene conjugate is produced by an inexpensive method, and a graphene conjugate is produced by an inexpensive transparent substrate. It can be integrated to produce an inexpensive transparent conductive base material.
The problems to be solved by the present invention are the above five problems.

A method for producing a transparent conductive base material having a structure in which a graphene junction composed of a collection of graphene obtained by joining the graphene flat surfaces on which the graphene flat surfaces are overlapped is thermocompression bonded to a synthetic resin transparent film is used.
A collection of scaly graphite particles or a collection of massive graphite particles is flatly packed on the surface of one of the two parallel plate electrodes, and the parallel plate electrode is immersed in methanol filled in a container. Further, the other parallel plate electrode is superposed on the one parallel plate electrode, and the two parallel plate electrodes are separated from each other through a collection of the scaly graphite particles or a collection of the massive graphite particles. , The two separated parallel plate electrodes are immersed in the methanol, and then a DC potential difference is applied to the gap between the two parallel plate electrodes, whereby the magnitude of the potential difference is increased to the above 2. An electric field corresponding to the value divided by the size of the gap between the parallel plate electrodes is applied to the collection of scaly graphite particles or the collection of lump graphite particles, and the application of the electric field causes the scaly graphite particles or All of the interlayer bonds of the basal plane forming the massive graphite particles are simultaneously destroyed, and a collection of graphenes corresponding to the basal plane is produced in the gap between the two parallel plate electrodes. The gap between the parallel plate electrodes is expanded, the two parallel plate electrodes are tilted in the methanol, and vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to the container to collect the graphite particles. The two parallel plate electrodes are moved into the methanol through the gap between the two parallel plate electrodes, and then the two parallel plate electrodes are taken out from the container, whereby a collection of the graphite is deposited in the methanol in the container. Graphite is produced,
Next, a transparent film of synthetic resin having the shape of the bottom surface of the container is placed on the bottom surface of the container for producing the transparent conductive base material, and the suspension produced by the above method is further subjected to the transparent conductive base material. The container is filled in an amount required for production, and then vibrations in three directions of front-back, left-right, and up-down are repeatedly applied to the container, whereby a collection of graphenes constituting the suspension is formed. The graphene moves in the methanol constituting the suspension with the flat surface of the graphene facing up, the graphene is diffused throughout the container, and the flat surfaces of the graphene are overlapped with each other via methanol. Is formed on the transparent film of the synthetic resin as the shape of the bottom surface of the container, and then a plate material having the size of the group of graphene is placed on the group of graphene, and further, the container is further placed. Is heated to the boiling point of methanol to vaporize the methanol, and then the plate material is compressed and the container is heated to the Vicat softening temperature of the synthetic resin constituting the transparent film.
As a result, after the methanol is vaporized, a collection of graphenes in which the flat surfaces of the graphenes are overlapped with each other is formed on the transparent film of the synthetic resin as the shape of the bottom surface of the container, and then the graphenes are formed. The collection is compressed, and frictional heat is generated at the portion where the flat surfaces of the graphene overlap each other. The frictional heat causes the flat surfaces of the graphene to join each other, and the flat surfaces of the graphene overlap each other. A graphene joint composed of a collection of the bonded graphenes is formed, the transparent film of the synthetic resin is softened, and the graphene joint is pressure-bonded to the surface of the transparent film of the softened synthetic resin, and the graphene joint is formed. Is heat-bonded to the transparent film of the synthetic resin to form a transparent conductive base material having the shape of the bottom surface on the bottom surface of the container. By repeatedly applying vibration in the direction and taking out the transparent conductive base material from the container, a graphene joint composed of a collection of the graphenes in which the flat surfaces of the graphenes overlap each other is formed of a synthetic resin. This is a method of a transparent conductive base material for producing a transparent conductive base material having a structure in which a transparent film is heat-bonded.

That is, the method for producing a transparent conductive base material in the present invention comprises the following three steps.
First, an aggregate of graphene is produced from an aggregate of graphite particles in methanol, and a suspension in which the aggregate of graphene is precipitated in methanol is produced. For this reason, a collection of scaly graphite particles or a collection of massive graphite particles narrowed in the gap between the two parallel plate electrodes is immersed in methanol, which is an insulator, and a direct current is applied between the two parallel plate electrodes. Apply a potential difference. As a result, an electric field corresponding to the value obtained by dividing the potential difference by the size of the gap between the two parallel plate electrodes is generated in the electrode gap where a collection of scaly graphite particles or a collection of massive graphite particles exists. This electric field simultaneously applies a Coulomb force sufficient for breaking the interlayer bond of the basal plane made of graphite crystals to all the above-mentioned graphite particles to all the π electrons that are responsible for the interlayer bond of the basal plane. As a result, the π electron is released from the constraint on the π orbital, and all the π electrons are separated from the π orbital and become free electrons. That is, when the Coulomb force acting on the π electron is given to the π electron as a force larger than the interaction of the π orbitals, the π electron is released from the constraint of the π orbital and becomes a free electron. As a result, all the π electrons that are responsible for the interlayer bonding of the basal plane do not exist in the π orbital, and for all the graphite particles, all the interlayer bonds of the basal plane forming the graphite particles are simultaneously destroyed. As a result, a collection of basal planes, that is, a collection of graphene, is instantly produced in the gap between the two parallel plate electrodes. The produced graphene is a genuine substance consisting only of graphite crystals without impurities, and a suspension in which a collection of the graphene is precipitated in methanol is produced in a container. Since the two parallel plate electrodes are immersed in methanol, the graphene deposited in the gap between the two parallel plate electrodes does not scatter. As a result, the first problem out of the five problems described in paragraph 9 was solved.
When a potential difference is applied between two parallel plate electrodes immersed in methanol, which is an insulator, an electric field is generated in the gap between the two parallel plate electrodes. That is, methanol is an insulator having a specific resistance of 3 MΩ · cm or more and a dielectric constant of 33. Ethanol is also an insulator having a dielectric constant of 24, and the electrical conductivity of ethanol is 7.5 × ^10-6 S / m. On the other hand, the electrical conductivity of the scaly graphite particles is 43.9 S / m. Thus, ethanol, compared to the scaly graphite particles is a conductor, the electric conductivity is 1.7 × 10 ⁷ times lower insulator. Further, in the present invention, methanol, which is an industrial alcohol having the lowest viscosity, the lowest boiling point, and the cheapest, is used as the alcohol.
Secondly, a transparent film of synthetic resin having the shape of the bottom surface is placed on the bottom surface of a container for producing a transparent conductive base material, and seven graphene flat surfaces are formed on the transparent film via methanol. As a smaller number, it forms a collection of overlapping graphenes. Therefore, a transparent film having the shape of the bottom surface of the container is placed on the bottom surface of the container, and the suspension produced by the above-mentioned production method is used in the container as an amount required for producing the transparent conductive base material. After filling, the container is repeatedly vibrated in three directions of front-back, left-right, and up-down to form a collection of graphenes on which the flat surfaces of graphenes are overlapped with each other via methanol. That is, since the thickness of graphene is extremely thin, the aspect ratio, which is the ratio of the surface area to the thickness, is extremely large. In addition, graphene is extremely thin and has almost no mass. When a three-way vibration is applied to a suspension in which a collection of graphene having these characteristics is precipitated in methanol, the graphene moves in the methanol with the flat surface facing up, and the graphene diffuses throughout the container. The flat planes overlap with each other via methanol. When the vibration to the container is stopped, a collection of graphene in which the flat surfaces are overlapped with each other via methanol is formed on the transparent film. The vibration acceleration applied to the container is about 0.2 G because graphene is extremely lightweight. Further, in forming the transparent conductive base material having the shape of the bottom surface on the bottom surface of the container, in order to give the transparent conductive base material more transparency than ITO, the number of graphene is set to be less than 7, and the graphene is flattened. Overlay the faces. Therefore, before forming the transparent conductive base material, the amount of the suspension to be filled in the container should be clarified. As a result, the second problem out of the five problems described in paragraph 9 was solved.
Third, the flat planes of graphene are joined to form a graphene joint, and the graphene joint is thermocompression bonded to a transparent film made of synthetic resin. Therefore, after vaporizing methanol from the container, a plate material having the size of the graphene aggregate is placed on the graphene aggregate to evenly compress the graphene aggregate, and the container is heated to the bicut softening temperature of the synthetic resin. The temperature rises to. At this time, when methanol is vaporized from the suspension, a collection of graphene in which flat surfaces are overlapped is formed on the transparent film. Next, frictional heat is generated at the portion where the graphene flat surfaces overlap each other, and the graphene flat surfaces are joined to each other by the frictional heat, and the graphene joint body in which the graphene flat surfaces are overlapped and joined is softened and transparent. Press onto the film. After that, the container is repeatedly vibrated in three directions of front-back, left-right, and up-down to peel off the transparent conductive base material whose graphene conjugate is thermocompression-bonded to the transparent film of synthetic resin from the container, and the transparent conductive base material is removed from the container. Take it out. The vibration acceleration applied to the container is about 0.2 G.
That is, graphene has a breaking strength of 42 N / m, which is a tough material having a strength more than 100 times that of steel. Therefore, even if an excessive compressive stress is applied to the plane above the graphene aggregate, the flat plane of graphene does not deform or break. On the other hand, the synthetic resin forming the transparent film has a large compressive strength. For example, it is 19-25 MPa for high-density polyethylene resin. 1 MPa corresponds to 9.8 kg weight / mm ^2, and corresponds to the compressive strength when a load of 9.8 kg is placed on a small area of 1 mm ² . Therefore, among the synthetic resins constituting the transparent film, even a high-density polyethylene resin having a relatively low compressive strength has a compressive strength of at least 186 kg weight / mm ² . The compressive strength of other synthetic resins forming a transparent film is 55-89 MPa for polyvinyl chloride resin, 140-190 MPa for polyvinyl chloride resin, 38-55 MPa for polypropylene resin, 76-103 MPa for polyethylene terephthalate resin, and polycarbonate. Resin is 69-86 MPa, polystyrene resin is 82-89 MPa, polymethyl methacrylate resin 73-125 MPa, polysulfone resin is 276 MPa, polyether sulfone resin is 81-108 MPa, polyetherimide resin is 140 MPa, all of which are high-density polyethylene resins. Higher compression strength. Therefore, even with a high-density polyethylene resin having a low compressive strength, the transparent film is not destroyed if the load is 186 kg or less with respect to an area of 1 mm ² . Therefore, the transparent film of the synthetic resin is not destroyed even if a large compressive stress is applied when joining the flat surfaces of graphene.
On the other hand, when the temperature of the thermoplastic resin is raised, the Vicat softening temperature is a guideline for the temperature at which the thermoplastic resin begins to soften rapidly. The bicut softening temperature is 70-80 ° C for the high-density polyethylene resin, 80-100 ° C for the polypropylene resin, 70-85 ° C for the polyvinyl chloride resin, 85-100 ° C for the polystyrene resin, and 90 for the polymethylmethacrylate resin. It is −110 ° C. and 142-146 ° C. for polypropylene resin. Both are higher than the boiling point of methanol, 65 ° C. Therefore, when the temperature is raised to the Vicat softening temperature, the transparent film begins to soften, and the softened transparent film is pressure-bonded to the graphene joint by compressive stress.
As a result, the third and fourth problems out of the five problems described in paragraph 9 were solved. The vaporized methanol is recovered by a recovery machine and reused.
By the way, methanol used in producing a graphene conjugate is an inexpensive industrial chemical. Graphite particles are also an inexpensive industrial material. In addition, the above-mentioned three steps consist of extremely simple processes. Therefore, according to this method, when inexpensive graphite particles and methanol are used and three extremely simple steps are carried out in succession, the graphene junction is thermocompression bonded to the transparent film. As a result, the fifth problem out of the five problems described in paragraph 9 was solved, and all the problems were solved.
The graphene conjugate produced by the method described above brings about the following effects.
First, since the transparent conductive base material is manufactured as the shape of the bottom surface of the container, the shape and area of the transparent conductive base material can be freely changed according to the shape of the bottom surface of the container. Therefore, there are no restrictions on the area and shape of the transparent conductive base material, and it can be used as a general-purpose transparent conductive base material.
Second, the graphene conjugate constituting one surface of the transparent conductive base material is composed of graphene only. Therefore, it has transparency, thermal conductivity, and electrical conductivity similar to graphene, and also has an antistatic function, an electromagnetic wave shielding function, and a heat dissipation function.
Third, the surface irregularities of the graphene joint are only 0.332 nm of the graphene thickness, which is close to a perfect flat surface. Therefore, one surface of the transparent conductive base material exhibits super water repellency with a contact angle close to 180 degrees, and this surface has water repellency, oil repellency, and antifouling property.
Fourth, since the graphene conjugate is as thin as 2.3 nm or less and has transparency, it is difficult to visually identify the presence of the graphene conjugate. However, the transparent conductive base material obtained by thermocompression bonding a transparent film to the graphene joint can be handled by human hands.
Here, in the first treatment, the interlayer bond of the basal plane made of graphite crystals forming graphite particles narrowed in the gaps between the two parallel plate electrodes by the electric field applied to the gaps between the two parallel plate electrodes. However, the phenomenon of being destroyed at the same time will be explained.
The carbon atom forming the graphite crystal in the graphite particles has four valence electrons. Three of these valence electrons are the basal plane, that is, the σ electrons that form graphene. These σ electrons covalently bond with the σ electrons of three adjacent carbon atoms on the basal plane at an angle of 120 degrees to form a strong hexagonal network structure two-dimensionally. The remaining one valence electron is a π electron, which exists in a π orbit extending in a direction perpendicular to the basal plane. The π-electrons are bonded to the π-electrons of adjacent carbon atoms in the vertical direction perpendicular to the basal plane with a weak bonding force, and the basal plane is laminated in layers based on this weak bonding force. That is, the basal plane, that is, graphene, is layered to each other by the interaction of π orbitals, which is a weak bonding force. Therefore, the graphite particles have a property of being easily peeled off at the basal plane made of graphite crystals, that is, having mechanical anisotropy. This mechanical anisotropy is well known as the lubricity of graphite particles.
When an electric field is applied to these graphite particles, a Coulomb force due to the electric field acts on all π electrons. When the Coulomb force acting on the π electron acts on the π electron as a force larger than the interaction of the π orbital acting on the π electron, the π electron is released from the constraint on the π orbit. As a result, all π electrons move away from the π orbital and become free electrons. As a result, all the π electrons that are the bearers of the interlayer bonding of the basal plane disappear from the π orbital, so that all the interlayer bonding of the basal plane is destroyed at the same time. That is, when the π electron moves a distance of the interlayer distance b of the basal plane by the Coulomb force F, the π electron performs work W (W = b · F). This work W is 35 millielectronvolts, which is the magnitude of the interaction of π orbitals per atom acting on π electrons (electron volt is a unit that expresses the magnitude of energy possessed by an electron, and 1 electron volt is 1. ^Beyond (corresponding to 62 × ^10-19 joules), the π electron is released from the constraint of the interaction of the π orbit and becomes a free electron. For example, if the gap between the two parallel plate electrodes is separated by 100 μm and a DC potential difference of 10.6 kilovolt or more is applied to the gap between the electrodes, the interlayer bond on the basal plane is instantly broken. As described above, a large amount of graphene can be inexpensively produced by an extremely simple means of applying an electric field to a collection of inexpensive graphite particles. Further, since all the interlayer bonds of the basal plane are broken at the same time, the obtained fine substance is graphene, which is the basal plane made of graphite crystals.
The group of graphite particles referred to here means a group of relatively small amounts of graphite particles of about 1 g to 100 g. That is, the scaly graphite particles or the massive graphite particles are fine particles having a bulk density of 0.2-0.5 g / cm ³ and a particle size of 1-300 microns. Therefore, it is easy to pull the aggregate of graphite particles into the gap between the two parallel plate electrodes, and it is also easy to apply a potential difference to the two parallel plate electrodes. When a potential difference is applied to the gap between the two parallel plate electrodes, an electric field is generated in all the regions where the graphite particles are attracted. This electric field acts on the π electron as a Coulomb force larger than the interaction of the π orbit, and the π electron is released from the constraint on the π orbit and becomes a free electron. As a result, all the interlayer bonds of the basal plane in the graphite particles are simultaneously broken, and a graphene aggregate is produced in the gap between the two parallel plate electrodes.
Here, the number of graphene dispersed in the suspension is calculated by arithmetic. Here, it is assumed that all graphite particles are composed of spheres having a diameter of 25 microns, and since the true density of graphite is 2.25 × 10 ³ kg / m ³ , the weight of one graphite particle is high. Is only 1.84 x ^10-8 g. Assuming that the average thickness of the graphite particles is 10 microns, the interlayer distance is 3.354 angstroms. Therefore, 297,265 graphenes are laminated on the scaly graphite particles having a thickness of 10 microns. .. Therefore, by breaking all the interlayer bonds on the basal plane, a collection of 297,265 graphenes can be obtained from only one spherical graphite particle. Therefore, for an aggregate of only 1 g of spherical graphite particles, an aggregate of 1.62 × 10 ¹³ graphenes can be obtained when all the interlayer bonds on the basal plane are broken. Therefore, according to this production method, an enormous number of graphene aggregates can be obtained from a small amount of graphite particles.

The method of forming a transparent electrode on the surface of a transparent conductive base material described in paragraph 10 is described.
A metal compound that precipitates a metal having a refractive index of 0.4 or more and 2.4 or less by thermal decomposition in the wavelength region of visible light is dispersed in methanol, and the metal compound is dispersed in the methanol in a molecular state. The first property of dissolving or mixing in the methanol, the second property having a viscosity higher than that of the methanol, the third property having a melting point lower than 20 ° C., and the boiling point are described above. An organic compound having a fourth property lower than the thermal decomposition temperature of the metal compound is mixed with the methanol dispersion to prepare a mixed solution in which the organic compound is uniformly mixed with the methanol dispersion, and the mixture is prepared. The liquid is applied or printed on the surface of the graphene conjugate constituting the transparent conductive base material produced by the production method described in paragraph 10, and the transparent conductive base material is heat-treated to thermally decompose the metal compound. The first feature is that the metal has a refractive index of 0.4 or more and 2.4 or less in the visible light wavelength region, and the particle size is one digit smaller than the visible light wavelength. A collection of metal fine particles having the second characteristic of the above is deposited all at once on the surface of the graphene junction to which the mixed solution is applied or printed, and the metal fine particles are metal-bonded at a portion where they come into contact with each other to form the metal. A collection of bonded metal fine particles is formed on the surface of the graphene joint to which the mixed solution is applied or printed, and then the surface of the graphene joint on which the collection of metal fine particles is formed is evenly compressed. While plastically deforming the collection of metal-bonded metal fine particles, frictional heat is generated at a portion where the collection of plastically deformed metal fine particles comes into contact with the surface of the graphene joint, and the plastically deformed metal is generated by the frictional heat. A collection of fine particles is bonded to the surface of the graphene junction, whereby a transparent electrode composed of the collection of metal fine particles is formed on the surface of the graphene junction constituting the transparent conductive substrate. It is a method of forming a transparent electrode on the surface of the above-described transparent conductive base material.

That is, the method of forming a transparent electrode composed of a collection of metal-bonded metal fine particles on a graphene junction, which is one surface of a transparent conductive base material, comprises the following five steps.
First, a metal compound that precipitates a metal having a refractive index of 0.4 or more and 2.4 or less in the wavelength region of visible light by thermal decomposition is dispersed in methanol, and the metal compound is methanol in a molecular state. The raw material of the metal fine particles is liquid-phased.
Second, an organic compound having four properties is mixed with a methanol dispersion to prepare a mixed solution in which the organic compound is uniformly mixed with the methanol dispersion.
Third, a mixed solution is applied or printed on the graphene joint, which is one surface of the transparent conductive base material, on the portion where the transparent electrode is formed, and a coating film or a printing film is applied with a thickness according to the viscosity of the mixed solution. Form. The viscosity of the mixed solution can be freely changed and the thickness of the coating film or the printing film can be freely changed according to the viscosity of the organic compound and the concentration of the organic compound in the mixed solution. Further, if the viscosity of the mixed solution is reduced, the shape and line width of the printing film during screen printing are not restricted. Further, there are no restrictions on the shape and size of the coating film or the printing film, and there are no restrictions on the shape and size of the transparent electrode, that is, the collection of metal fine particles bonded to the graphene joint.
Fourth, the coating film or the printing film is heat-treated to thermally decompose the metal compound. At this time, the following phenomenon occurs in accordance with the temperature rise. First, when the boiling point of methanol is reached, methanol is vaporized from the coating film or printed film. At this time, since the metal compound is dispersed in methanol but not in the organic compound, the fine crystals of the metal compound are precipitated all at once in the organic compound, and the fine crystals are uniformly precipitated in the organic compound in the coating film or the printed film. It becomes turbid. Next, when the boiling point of the organic compound is reached, the organic compound is vaporized from the coating film or the printed film. The vaporized organic compound is recovered and reused. As a result, the coating film or the printing film becomes a collection of fine crystals of the metal compound. The size of the fine crystals is close to the size of the metal fine particles of 40-60 nm precipitated by the thermal decomposition of the metal compound. Further, when the temperature at which the metal compound is thermally decomposed is reached, the fine crystals are thermally decomposed, and the fine crystals of the metal compound are decomposed into an inorganic substance or an organic substance and a metal, and after vaporization of the inorganic substance or the organic substance, the size is 40-60 nm. A collection of metal fine particles having both the first characteristic of being granular fine particles of the above and the second characteristic of a metal having a refractive index of 0.4 or more and 2.4 or less in the wavelength region of visible light. , The coating film or the printing film is formed all at once on the graphene bond. The metal fine particles are precipitated in an active state without impurities, and metal bonds are formed at the sites where the metal fine particles are in contact with each other, and a collection of metal-bonded metal fine particles is formed in a graphene junction. As a result, the collection of metal fine particles has transparency and conductivity.
Fifth, the upper plane of the graphene junction in which the metal-bonded metal fine particles are formed is evenly compressed to plastically deform the metal-bonded metal fine particles, and the plastic-deformed metal fine particles are formed. A frictional heat is generated at a portion in contact with the graphene joint, and the frictional heat joins a collection of plastically deformed metal fine particles to the graphene joint. As a result, a collection of metal-bonded metal fine particles is bonded to the graphene junction, and a transparent electrode composed of a collection of metal fine particles is bonded to the surface of the graphene junction. Since the metal fine particles are made of a genuine metal without impurities and the graphene junction is also a genuine substance without impurities, the metal fine particles are firmly bonded to the graphene junction.
The process of joining the aggregate of metal fine particles described above to the graphene joint is extremely simple, and the material used is an inexpensive industrial chemical. As a result, a collection of metal fine particles can be bonded to an inexpensive transparent conductive base material by an inexpensive method, an inexpensive transparent electrode is formed on the transparent conductive base material, and the transparent conductive base material can be used for various purposes. ..
If the transparent film of the synthetic resin does not thermally decompose at the temperature at which the metal compound thermally decomposes, the transparent film does not change irreversibly, maintains its original physical properties, and is graphene bonded on one surface of the transparent conductive substrate. A transparent electrode made of a collection of metal-bonded metal fine particles can be formed on the body. Therefore, a transparent film made of a synthetic resin having a higher thermal decomposition temperature than the thermal decomposition temperature of the metal compound is used.
The transparent electrode formed on the transparent conductive base material described above brings about the following effects.
First, since the raw material of the metal fine particles precipitated by thermal decomposition is made into a paint, there is no restriction on the size and shape of the transparent electrode, that is, the collection of the metal fine particles to be bonded to the graphene joint. In addition, the viscosity of the paint can be freely adjusted, and there are no restrictions when applying or printing the paint.
Second, the metal fine particles are precipitated as a genuine metal without impurities. On the other hand, by the time the graphene conjugate is taken out of the container and the mixed solution is applied to the surface of the graphene conjugate, low boiling point impurities such as water molecules, hydroxyl groups and organic substances may adhere to the surface of the graphene conjugate. .. However, when methanol is vaporized from the coating film or printed film, and then the pyrolysis product of the metal compound is vaporized, these impurities are vaporized in the order of boiling points, and the graphene conjugate is as if it was manufactured in a container. , Return to a genuine substance without impurities. Further, when the methanol and the thermal decomposition product of the metal compound are vaporized, the portion where the coating film or the printing film is formed has a relatively positive pressure from the outside, so that the coating film or the printing film is formed. The surface of the graphene bonded body is not invaded by impurities and adsorbed again. For this reason, a collection of metal fine particles made of an intrinsic metal is firmly bonded to a graphene conjugate made of an intrinsic substance.
Third, in the wavelength region of visible light, the refractive index of metal is 0.4 or more and 2.4 or less, which is close to the refractive index of air 1, so that 70% or more of visible light is metal-bonded metal fine particles. It is incident on the gathering of. Further, since the size of the metal fine particles is an order of magnitude smaller than the wavelength of the visible light, the visible light is not scattered in the collection of the metal fine particles and is transmitted through the collection of the metal fine particles with high transparency. As a result, a collection of metal-bonded metal fine particles constitutes a transparent electrode.
Fourth, a collection of metal-bonded metal fine particles can be bonded to a graphene junction by using an inexpensive material and by an inexpensive method, and an inexpensive transparent electrode can be formed on the surface of the graphene junction.
As described above, according to this method, a transparent electrode can be formed on the surface of the transparent conductive base material. As a result, a transparent conductive film that can be applied to various uses such as a transparent conductive film for a touch panel, a flexible circuit board, a transparent conductive film of an organic EL, a transparent conductive film of an organic thin-film solar cell, and a flexible LED conductive film can be manufactured at low cost.
The surface reflectance and total light transmittance of visible light in a collection of metal-bonded metal fine particles will be described in paragraph 14 below, and the scattering of light in a collection of metal fine particles will be described in paragraph 15 below. ..

Here, the surface reflectance and the total light transmittance will be described. When light enters the substrate, surface reflection occurs according to the difference in refractive index between the air and the substrate. Therefore, even with transparent glass, loss due to surface reflection occurs, and the total light transmittance does not reach 100%. By the way, in the float glass having a thickness of 2 mm, the total light transmittance is about 90% in the wavelength region of visible light. The surface reflectance R on the surface of light vertically incident on the base material is calculated by Equation 1 consisting of the refractive index n of the base material and the refractive index m of air. Further, the total light transmittance T is calculated by the mathematical formula 2 composed of the surface reflectance R. Therefore, when the refractive index of the metal is 0.4, the total light transmittance incident on the transparent electrode is 67%, and when the refractive index of the metal is 2.4, the total light transmittance incident on the transparent electrode is 67%. Is 69%, and 70% or more of visible light is incident on the conductive layer.
Number 1
R = (nm) ² / (n + m) ²
Number 2
T = (1-R) ²

Next, light scattering will be described. The Rayleigh scattering formula shown in Equation 3 can be applied to the scattering of light when visible light is applied to a collection of particles. In Equation 3, S is the scattering coefficient, which means the ratio of scattering, λ is the wavelength of visible light, D is the particle diameter, m is the refractive index of the particle, and π is the pi. Therefore, the magnitude of the scattering coefficient S depends on the ratio D / λ of the particle diameter D to the wavelength λ of visible light to the fourth power, and also depends on the square of the particle diameter D and the refractive index m. Since the size D of the metal fine particles is an order of magnitude smaller than the wavelength λ of visible light, the ratio D / λ is small, and the particle diameter D is also sufficiently small. Further, the refractive index m of the metal is 0.4 or more and 2.4 or less. Therefore, the scattering coefficient S is extremely small, visible light is not scattered in the collection of metal fine particles, and the transparent electrode composed of the collection of metal fine particles exhibits high transparency.
Number 3
^{S = 4/3 · π 5} / λ 4 · D 6 {(m 2 -1) / (m 2 +1)} 2

The method of forming a transparent electrode on the surface of the transparent conductive base material described in paragraph 12 is described.
The metal compound described in paragraph 12 thermally decomposes granular fine particles of metal having both the first characteristic that the metal is composed of nickel or aluminum and the second characteristic that the size of the fine particles is an order of magnitude smaller than the wavelength of visible light. A metal compound that precipitates, wherein the metal compound is used as the metal compound described in paragraph 12 to form a transparent electrode according to the method of forming a transparent electrode on the surface of a transparent conductive substrate described in paragraph 12. It is a method of forming a transparent electrode on the surface of the transparent conductive base material described in 1.

That is, nickel or aluminum has a refractive index of 0.4 or more and 2.4 or less in the wavelength region of visible light (380-750 nm), and 70% or more of visible light is a collection of the metal-bonded metal fine particles described above. Incident in. Further, the size of the fine particles made of nickel or aluminum is an order of magnitude smaller than the wavelength of the visible light, and the scattering coefficient S of the visible light in the above-mentioned collection of metal-bonded metal fine particles is extremely small. , Visible light does not scatter and shows high transparency. As a result, the collection of metal-bonded metal fine particles forms a transparent electrode.
That is, the refractive index of nickel is 1.61 at 380 nm, increases with increasing wavelength, and is 1.75 at 539 nm, 2.21 at 709 nm, 2.28 at 729 nm, and 2.34 at 750 nm. On the other hand, light rays are reflected on the surface of a collection of nickel fine particles due to the difference in refractive index between air and nickel. At this time, the transmittance of light rays is 89% at 380 nm, 86% at 539 nm, 74% at 709 nm, 72% at 729 nm, and 70% at 750 nm. Further, the size of the nickel fine particles is an order of magnitude smaller than the wavelength of visible light. Therefore, a part of the component of the red visible light is reflected on the surface of the collection of nickel fine particles, but the light ray that has entered the collection of nickel fine particles passes through the collection of nickel fine particles without being scattered. Therefore, the collection of nickel fine particles shows transparency.
In addition, the refractive index of aluminum is 2.80, which is the maximum at 800 nm, and decreases sharply as the wavelength becomes shorter. It becomes 0.45 at 0.620 and 380 nm. On the other hand, on the surface of a collection of aluminum fine particles, light rays are reflected due to the difference in refractive index between air and aluminum. At this time, the transmittance of light rays is 69% at 750 nm, 81% at 708 nm, 100% at 560 nm, 89% at 450 nm, and 73% at 380 nm. Further, the size of the aluminum fine particles is an order of magnitude smaller than the wavelength of visible light. Therefore, a part of the visible light of red and purple is reflected on the surface of the collection of aluminum fine particles, but the light that has entered the collection of aluminum fine particles passes through the collection of aluminum fine particles without being scattered. Therefore, the collection of aluminum fine particles exhibits transparency.
As described above, when the metal is aluminum, some of the visible light of red and purple is reflected on the surface of the aggregate of aluminum fine particles, and when the metal is nickel, it is red. Some of the light rays that make up the visible light are reflected on the surface of a collection of nickel fine particles and emit a color corresponding to these light rays, but the collection of metal fine particles is transparent because it does not scatter visible light.
Further, the collection of nickel or aluminum fine particles has the following effects based on the size and material of the fine particles.
First, the surface is formed with irregularities based on the size of the metal fine particles. Since the total surface area of the uneven surface is an enormous number of metal fine particles forming the surface, the surface area has an enormous amount of surface area, which is close to a so-called fractal surface. When a droplet comes into contact with such a surface, the liquid does not enter the unevenness of the size of the metal fine particles due to the surface tension of the droplet, and the liquid surface of the droplet comes into contact with the convex portion of a huge number of fine particles by point contact. .. As a result, the surface of the transparent electrode exhibits super water repellency with a contact angle close to 180 degrees, and the surface is provided with water repellency, oil repellency, and stain resistance.
Secondly, it has conductivity and thermal conductivity close to those of nickel or aluminum. Therefore, the transparent electrode has an antistatic function, an electromagnetic wave shielding function, and a heat dissipation function.

The method of forming a transparent electrode on the surface of the transparent conductive base material described in paragraph 12 is described.
The metal compound described in paragraph 12 is a complex composed of an inorganic metal compound having a metal complex ion in which a ligand composed of an inorganic molecule or an ion is coordinated to a metal ion composed of nickel or aluminum. The described organic compound is any one kind of organic compound belonging to carboxylic acid esters, glycols or glycol ethers, and these two kinds of substances are used to be transparent on the surface of the transparent conductive substrate described in paragraph 12. A method of forming a transparent electrode on the surface of a transparent conductive substrate described in paragraph 12, wherein a transparent electrode is formed according to a method of forming an electrode.

That is, the complex composed of the inorganic metal compound is thermally decomposed at a relatively low temperature of 180 ° C.-220 ° C. in the reducing atmosphere to precipitate a metal. Further, it is dispersed in methanol, which is the most general-purpose alcohol, at a ratio close to 10% by weight. Therefore, the complex composed of the inorganic metal compound becomes a raw material for producing the mixed solution described in paragraph 12.
That is, when a complex composed of an inorganic metal compound having a metal complex ion in which a ligand composed of an inorganic molecule or an ion is coordinated to a metal ion is heat-treated in a reducing atmosphere, the coordination bond portion is first divided. It is decomposed into inorganic substances and metals. When the temperature is further raised, the inorganic substances take away the heat of vaporization and vaporize, and the metal precipitates after the vaporization of all the inorganic substances is completed. That is, among the ions constituting the complex, the metal ion located in the center of the molecule is the largest. Therefore, the distance between the metal ion and the ligand is the longest. Therefore, when the complex is heat-treated in a reducing atmosphere, the coordination bond portion in which the metal ion binds to the ligand is first separated and decomposed into a metal and an inorganic substance. When the temperature rises further, the inorganic substances take away the heat of vaporization and vaporize, and after the vaporization is completed, the metal precipitates. At this time, since the inorganic substance has a low molecular weight, vaporization of the inorganic substance is completed at a low temperature of 180-220 ° C. according to the molecular weight of the inorganic substance. As such a complex, a complex composed of an inorganic metal compound having an ammine metal complex ion in which ammonia NH ₃ serves as a ligand and coordinates to a metal ion, chlorine ion Cl ⁻ , or chlorine ion Cl ⁻ and ammonia NH _A complex composed of an inorganic metal compound having a chlorometal complex ion in which 3 acts as a ligand and coordinates with a metal ion, and a cyano group CN ⁻ serves as a ligand ion and coordinates with a metal ion. A complex composed of an inorganic metal compound having a complex ion, a complex composed of an inorganic metal compound having a bromometal complex ion in which a bromine ion Br ⁻ becomes a ligand ion and coordinates to a metal ion, and an iodine ion I ⁻ are coordinated. There are complexes composed of inorganic metal compounds having iodo metal complex ions that become child ions and coordinate-bond to metal ions. Further, such a complex composed of an inorganic metal compound having a small molecular weight is a metal complex having a metal complex ion which is easy to synthesize and is the cheapest.
In addition, the first property of dissolving or mixing in methanol with carboxylic acid esters, glycols or glycol ethers, the second property of viscosity higher than that of methanol, and melting point lower than 20 ° C. There are organic compounds having a third property and a fourth property having a boiling point lower than the thermal decomposition temperature of the complex composed of the inorganic metal compound. All of these organic compounds are general-purpose industrial chemicals. Therefore, such an organic compound becomes an inexpensive raw material for producing the mixed solution described in paragraph 12.
Therefore, when any one of the above-mentioned organic compounds is mixed with the methanol dispersion of the complex composed of the inorganic metal compound, the complex and the organic compound are uniformly mixed in the molecular state, and a large amount of the mixed solution is produced. As a result, a complex composed of an inorganic metal compound, which is an inexpensive industrial chemical, methanol, which is the most general-purpose alcohol, and an organic compound, which is a general-purpose industrial chemical, are used as raw materials, and 12 paragraphs are inexpensive. The mixed solution described in 1 is produced.
Most of the synthetic resins constituting the transparent film do not thermally decompose at a temperature of 180 ° C.-220 ° C. in a reducing atmosphere. Therefore, a ligand composed of an inorganic molecule or an ion thermally decomposes a complex composed of an inorganic metal compound having a metal complex ion coordinated to a metal ion composed of nickel or aluminum, thereby irreversibly changing the transparent film. A transparent electrode is formed on the surface of the transparent conductive base material without causing the problem. That is, when the thermal decomposition of the synthetic resin starts, the molecular structure of the polymer changes irreversibly, and the physical properties of the synthetic resin cannot be restored. Therefore, if the thermal decomposition of the synthetic resin does not start by the thermal decomposition of the complex composed of the inorganic metal compound, the transparent electrode is formed on the surface of the transparent conductive base material without irreversibly changing the transparent film.

The method of forming a transparent electrode on the surface of the transparent conductive base material described in paragraph 12 is described.
The metal compound described in paragraph 12 has the first characteristic that the oxygen ion constituting the carboxyl group in the carboxylic acid is covalently bonded to the metal ion composed of nickel or aluminum, and the second characteristic that the carboxylic acid is composed of a saturated fatty acid. It is a carboxylic acid metal compound having the characteristics of the above, and the organic compound described in paragraph 12 is any one kind of organic compound belonging to carboxylic acid esters, glycols or glycol ethers, and these two kinds of substances. Is a method of forming a transparent electrode on the surface of the transparent conductive base material described in paragraph 12 according to the method of forming a transparent electrode on the surface of the transparent conductive base material described in paragraph 12.

That is, the metal carboxylate compound having two characteristics is thermally decomposed at 290-430 ° C. in the air atmosphere to precipitate a metal. Further, it is dispersed in a concentration close to 10% by weight with respect to methanol, which is the most general-purpose alcohol. Therefore, the metal carboxylate compound becomes a raw material for producing the mixed solution described in paragraph 12. The thermal decomposition temperature of the metal octylate compound is 290 ° C. in the air atmosphere, and the thermal decomposition temperature is the lowest among the metal carboxylate compounds. That is, since the boiling point of octyl acid is the lowest among the carboxylic acids, the thermal decomposition temperature of the metal octylate compound is the lowest. On the other hand, the thermal decomposition temperature of the metal octylate compound in the nitrogen atmosphere is 340 ° C., which is 50 ° C. higher than that in the atmospheric atmosphere.
That is, in the carboxylic acid metal compound having both the first characteristic that the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion and the second characteristic that the carboxylic acid is composed of a saturated fatty acid, the metal ion is present. The distance between the oxygen ion, which is the largest ion and constitutes a carboxyl group, and the metal ion is longer than the distance between other ions. When a metal carboxylic acid compound having such molecular structural characteristics is heat-treated in an air atmosphere, when the boiling point of the carboxylic acid is exceeded, the bond portion between the oxygen ion and the metal ion constituting the carboxyl group is first separated to form the carboxylic acid. Separate into metal. Furthermore, when the carboxylic acid is composed of saturated fatty acids, the carboxylic acid does not have an unsaturated structure in which carbon atoms are excessive with respect to hydrogen atoms, so that the carboxylic acid generates heat of vaporization depending on the molecular weight and number of the carboxylic acid. It is deprived and vaporized, and when vaporization is completed, metal precipitates. Examples of such metal carboxylate compounds include metal octylate compounds, metal laurate compounds, and metal stearate compounds. The boiling point of octyl acid is 228 ° C, the boiling point of lauric acid is 296 ° C, and the boiling point of stearic acid is 361 ° C. Therefore, these metal carboxylate compounds are thermally decomposed in an air atmosphere of 290-430 ° C. Further, it is dispersed in methanol at a ratio close to 10% by weight. The thermal decomposition of the metal carboxylate compound in a nitrogen atmosphere shifts to a high temperature side of about 50 ° C.
Further, the metal carboxylate compound is an inexpensive industrial chemical that can be easily synthesized. That is, when a carboxylic acid, which is the most general-purpose organic acid, is reacted with a strong alkali, an alkali metal carboxylate compound is produced, and when the alkali metal carboxylate compound is reacted with an inorganic metal compound, a metal carboxylate compound is synthesized. To. Therefore, it is the cheapest organometallic compound among the organometallic compounds. Therefore, the heat treatment temperature is higher than that of the complex composed of the inorganic metal compound described in paragraph 16, but the metal compound is cheaper than the complex.
In addition, the first property of dissolving or mixing in methanol with carboxylic acid esters, glycols or glycol ethers, the second property of viscosity higher than that of methane, and the third property of melting point lower than 20 ° C. There is an organic compound having the above-mentioned property and a fourth property having a boiling point lower than the thermal decomposition temperature of the metal carboxylate compound. Such organic compounds are general-purpose industrial chemicals. Therefore, such an organic compound becomes an inexpensive raw material for producing the mixed solution described in paragraph 12.
Therefore, when any one of the organic compounds is mixed with the methanol dispersion of the metal carboxylate compound, the metal carboxylate compound and the organic compound are uniformly mixed in a molecular state, and a large amount of the mixed solution is produced. As a result, a metal carboxylate compound, which is an inexpensive industrial chemical, methanol, which is the most general-purpose alcohol, and an organic compound, which is a general-purpose industrial chemical, are used as raw materials, and are described in paragraph 12 at an inexpensive cost. The mixed solution is produced.
In addition, as a synthetic resin constituting a transparent film, there is a synthetic resin which does not thermally decompose at 340 ° C. in a nitrogen atmosphere. That is, the thermal decomposition reaction of the polymer constituting the synthetic resin is significantly different between the atmosphere in which oxygen gas is present and the nitrogen atmosphere. The thermal decomposition of a polymer in an atmosphere in which oxygen gas is present is accompanied by heat generation because it is a thermal decomposition due to an oxidation reaction. This heat generation phenomenon promotes the thermal decomposition of a polymer composed of an organic substance that is easily oxidized. On the other hand, in the thermal decomposition in a nitrogen atmosphere, the oxidation reaction does not occur, the thermal decomposition due to the endothermic reaction occurs, and the exothermic phenomenon does not occur. Therefore, the temperature at which the polymer starts thermal decomposition shifts to the high temperature side with a significant delay compared to the atmosphere in which the oxygen gas is present. For example, the thermal decomposition of the high-density polyethylene resin starts at around 250 ° C. in the air atmosphere, whereas it starts at around 400 ° C. in the nitrogen atmosphere, and shifts to the high temperature side by 150 ° C. As for the thermal decomposition of other polymers in the nitrogen atmosphere, the polystyrene resin starts thermal decomposition at 350 ° C. and ends at around 460 ° C. The polyethylene terephthalate resin starts thermal decomposition at 425 ° C and ends at around 480 ° C. The polypropylene resin begins thermal decomposition at 370 ° C and ends at around 500 ° C. The high-density polyethylene resin begins thermal decomposition at 400 ° C and ends at around 520 ° C. Therefore, a transparent film made of a synthetic resin that does not thermally decompose at 340 ° C. in a nitrogen atmosphere can form a transparent electrode by thermally decomposing the metal octylate compound. Therefore, a transparent film made of unstretched polypropylene film, stretched polystyrene film, PET film, PES film, PTFE film, polycarbonate film and the like can be used.

It is the figure which enlarged and schematically represented a part of the side surface of the graphene junction in which the flat planes of graphene overlapped.

Embodiment 1
In this embodiment, firstly, it is dissolved or mixed with methanol, secondly, it has a higher viscosity than methanol, thirdly, it has a melting point lower than 20 ° C., and fourthly, it is either a complex composed of an inorganic metal compound or a metal octylate compound. This is an embodiment relating to an organic compound having these four properties, which has a boiling point lower than the temperature at which one of them thermally decomposes.
That is, if the boiling point of the organic compound is lower than around 180-220 ° C. at which the complex composed of the inorganic metal compound is thermally decomposed, the organic compound constitutes a mixed solution together with the methanol dispersion of the complex composed of the inorganic metal compound. If the boiling point of the organic compound is lower than 290 ° C. at which the metal octylate is thermally decomposed, a mixed solution is formed together with the methanol dispersion of the metal octylate. Therefore, the organic compound becomes an adjusting agent for adjusting the viscosity in the mixed solution. Most of the organic compounds having these four properties are present in organic compounds belonging to carboxylic acid esters, glycols, or glycol ethers.

The carboxylic acid esters are composed of three types: esters with saturated carboxylic acids, esters with unsaturated carboxylic acids, and esters with aromatic carboxylic acids.
Among saturated carboxylic acids, acetic acid esters having a small molecular weight include methyl cyclohexyl acetate having a melting point lower than 20 ° C., dissolving in methanol, having a viscosity four times that of methanol, and having a boiling point of 182 ° C. Therefore, among acetic acid esters having a molecular weight smaller than that of methylcyclohexyl acetate, there are acetic acid esters having a melting point lower than 20 ° C., dissolving in methanol, having a viscosity higher than that of methanol, and having a boiling point lower than 180 ° C.
Further, among saturated fatty acids, methyl laurate is an ester of lauric acid and methanol having a large molecular weight. Methyl laurate has a melting point lower than 20 ° C., is soluble in methanol, has a viscosity 4.4 times that of methanol, and has a boiling point of 262 ° C. Therefore, among saturated fatty acid esters having a larger molecular weight than methyl cyclohexyl acetate and a smaller molecular weight than methyl laurate, there are esters that are soluble in methanol, have a higher viscosity than methanol, and have a boiling point lower than 290 ° C.
On the other hand, butyl acrylate, which is an unsaturated carboxylic acid with a small molecular weight, has a viscosity twice that of methanol and a boiling point of 148 ° C, and 2-ethylhexyl acrylate, which has a viscosity twice that of methanol and a boiling point of 214 ° C. and so on. Both have a melting point lower than 20 ° C. and dissolve in methanol.

Glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Ethylene glycol is a liquid monomer having a melting point lower than 20 ° C., soluble in methanol, a viscosity 36 times higher than that of methanol, and a boiling point of 197 ° C. Diethylene glycol is a liquid monomer having a melting point lower than 20 ° C., dissolved in methanol, a viscosity 61 times higher than that of methanol, and a boiling point of 244 ° C. Propylene glycol is a liquid monomer having a melting point lower than 20 ° C., miscible with methanol, a viscosity 82 times higher than that of methanol, and a boiling point of 188 ° C. Dipropylene glycol is a liquid monomer that is miscible with methanol, has a viscosity 127 times higher than that of methanol, and has a boiling point of 232 ° C. Tripropylene glycol is a liquid monomer that is miscible with methanol, has a viscosity as high as 97 times that of methanol, and has a boiling point of 265 ° C. Since a polymerization inhibitor or a polymerization inhibitor that does not cause a polymerization reaction by light or heat is added to such a liquid monomer, the polymerization reaction does not occur by raising the temperature.

Glycol ethers include ethylene glycol ethers, propylene glycol ethers, and dialkyl glycol ethers in which the hydrogen at the end of ethylene glycol, diethylene glycol, or triethylene glycol is substituted with an alkyl group.
Among ethylene glycol-based ethers, glycol ethers, which have a melting point lower than 20 ° C and are soluble in methanol and have a lower boiling point than the thermal decomposition temperature of a complex composed of an inorganic metal compound, have a viscosity three times that of methanol and a boiling point of 125 ° C. Methyl glycol, isopropyl glycol with a viscosity of 5 times that of methanol and a boiling point of 142 ° C, butyl glycol with a viscosity of 6 times that of methanol and a boiling point of 171 ° C, isobutyl glycol with a viscosity of 5 times that of methanol and a boiling point of 161 ° C, viscosity. There are allyl glycols that are 4 times as thick as methanol and have a boiling point of 159 ° C, methyldiglycols that are 6.6 times as viscous as methanol and have a boiling point of 194 ° C, and hexyl glycols that are 8.8 times as viscous as methanol and have a boiling point of 208 ° C. To do.
Among ethylene glycol-based ethers, glycol ethers, which have a melting point lower than 20 ° C., are soluble in methanol, and have a lower boiling point than the thermal decomposition temperature of metal octylate, have a viscosity 12.7 times that of methanol and a boiling point. Methyltriglycol at 249 ° C, isopropyldiglycol with a viscosity of 8.3 times that of methanol and a boiling point of 207 ° C, butyldiglycol with a viscosity of 11 times that of methanol and a boiling point of 231 ° C, and a viscosity of 13.7 times that of methanol. Butyl triglycol having a boiling point of 271 ° C., isobutyl diglycol having a viscosity of 8.8 times that of methanol and having a boiling point of 220 ° C., a viscosity of 14.6 times that of methanol and having a boiling point of 259 ° C. hexyl diglycol, and a viscosity of 12. 2-ethylhexyl glycol with a viscosity of 9 times and a boiling point of 229 ° C, 2-ethylhexyldiglycol with a viscosity of 17.6 times that of methanol and a boiling point of 272 ° C, phenyl glycol with a viscosity of 52 times that of methanol and a boiling point of 245 ° C. There is a benzyl glycol that is 20 times more than methanol and has a boiling point of 256 ° C. Benzyl diglycol having a viscosity 33 times that of methanol and a boiling point of 302 ° C. is dissolved in methanol and has a boiling point higher than the thermal decomposition temperature of the metal octylate compound.
Next, among propylene glycol-based ethers, glycol ethers having a melting point lower than 20 ° C., dissolved in methanol, and having a lower boiling point than the thermal decomposition temperature of a complex composed of an inorganic metal compound have a viscosity 3.2 times that of methanol. Methylpropylene glycol with a boiling point of 121 ° C, methylpropylene glycol acetate with a viscosity of 2.2 times that of methanol and a boiling point of 146 ° C, propylpropylene glycol with a viscosity of 4.7 times that of methanol and a boiling point of 150 ° C, and a viscosity of methanol. There are butylpropylene diglycol having a viscosity of 5.8 times that of methanol and a boiling point of 170 ° C., and methylpropylene diglycol having a viscosity of 6.9 times that of methanol and having a boiling point of 187 ° C.
Among propylene glycol-based ethers, glycol ethers, which have a melting point lower than 20 ° C., dissolve in methanol, and have a lower boiling point than the thermal decomposition temperature of metal octylate, have a viscosity 18.3 times that of methanol and a boiling point. Propylpropylene diglycol at 212 ° C, butylpropylene diglycol with a viscosity of 12.5 times that of methanol and a boiling point of 231 ° C, phenylpropylene glycol with a viscosity of 39.3 times that of methanol and a boiling point of 243 ° C, and a viscosity of 13 of methanol. There is butylpropylene triglycol with a viscosity of 9.9 times and a viscosity of 274 ° C.
Finally, among dialkyl glycol ethers, glycol ethers, which have a boiling point lower than 20 ° C, dissolve in methanol, and have a boiling point lower than the thermal decomposition temperature of a complex composed of an inorganic metal compound, have a viscosity 1.9 times that of methanol. , Dimethyl glycol with boiling point 85 ° C, viscosity 3.4 times that of methanol, dimethyl diglycol with boiling point 162 ° C, viscosity 1.9 times that of methanol, boiling point 171 ° C dimethylporopylene diglycol, viscosity Is 21 times that of methanol and has a boiling point of 176 ° C., methyl ethyl diglycol, and has a viscosity of 2.4 times that of methanol and has a boiling point of 189 ° C.
Among dialkyl glycol ethers, glycol ethers having a melting point lower than 20 ° C., which dissolves in methanol and has a boiling point lower than the thermal decomposition temperature of the metal octylate compound, have a viscosity 6.4 times that of methanol and a boiling point of 216. There are dimethyltriglycols at ° C. and dibutyldiglycols having a viscosity 4.1 times that of methanol and a boiling point of 255 ° C.
As described above, among the carboxylic acid esters, glycols, and glycol ethers, there are many organic compounds having the four properties described in paragraph 20.

Embodiment 2
This embodiment is an embodiment of a complex composed of an inorganic metal compound described in paragraph 16, and as a metal compound that thermally decomposes at a low temperature to precipitate a metal, a ligand composed of an inorganic molecule or an ion is a metal ion. Explain that a metal complex having a metal complex ion coordinated to is suitable. That is, since the metal complex has a small molecular weight of the inorganic substance, it is thermally decomposed at a temperature at which the heat treatment temperature in the reducing atmosphere is relatively low. Here, a nickel compound in which nickel is used as a metal and nickel is precipitated by thermal decomposition will be described.
First, a nickel compound dispersed in methanol will be described. Nickel sulfate and nickel chloride are soluble in water, nickel ions are dissolved, and many nickel ions cannot participate in nickel precipitation. Also, nickel hydroxide and nickel oxide do not disperse in methanol. Therefore, such an inorganic nickel compound having a low molecular weight is not suitable as a raw material for precipitating nickel.
Next, a nickel compound that precipitates nickel by thermal decomposition will be described. Among the chemical reactions in which nickel is produced from nickel compounds, the chemical reaction by the simplest treatment is the thermal decomposition reaction. That is, just by raising the temperature of the nickel compound, the nickel compound is thermally decomposed and nickel is precipitated. Further, if the thermal decomposition temperature of the nickel compound is low, the heat treatment temperature is low, so that the transparent electrode can be formed at low cost. An inorganic nickel complex having a nickel complex ion coordinated to a nickel ion located in the center of the molecular structure with a molecule or ion composed of an inorganic substance as a ligand is thermally decomposed in a reducing atmosphere if the molecular weight of the inorganic substance is small. The temperature at which the organic nickel complex having a larger molecular weight forms a ligand is lower than the temperature at which the organic nickel complex thermally decomposes in an atmospheric atmosphere. Therefore, although the inorganic nickel complex is a relatively expensive substance as compared with the organic nickel complex, nickel is precipitated at a lower temperature, so that a transparent electrode can be formed at a low cost.
That is, the nickel ion is the largest among the molecules constituting the inorganic nickel complex. By the way, the covalent radius of the nickel atom is 101 pm, while the covalent radius of the nitrogen atom is 71 pm, and the covalent radius of the oxygen atom is 66 pm. Therefore, in the molecular structure of the inorganic nickel complex, the distance of the coordination bond portion where the ligand is coordinated to the nickel ion is the longest. Therefore, in the heat treatment of the reducing atmosphere, the coordination bond portion is first separated, decomposed into nickel and an inorganic substance, and nickel is precipitated after the vaporization of the inorganic substance is completed.
Among such inorganic nickel complexes, ammonia NH ₃ serves as a ligand to coordinate bond with nickel ions, an ammine complex, chlorine ion Cl ⁻ , or chlorine ion Cl ⁻ and ammonia NH ₃ are coordinated. A chloro complex that becomes a child and coordinates with a nickel ion is relatively easy to synthesize as compared with other nickel complexes, and therefore can be produced at a relatively low production cost. Further, when such an inorganic nickel complex is heat-treated in a reducing atmosphere such as ammonia gas or hydrogen gas, the coordination bond site is first divided at a temperature lower than 200 ° C. because the molecular weight of the ligand is small, and then Nickel precipitates at a temperature of around 200 ° C. Further, it is dispersed in methanol to nearly 10% by weight. Such nickel complex ions include, for example, hexaammine nickel ion [Ni (NH ₃ ) ₆ ] ²⁺ , and nickel complexes include, for example, hexaammine nickel chloride [Ni (NH ₃ ) ₆ ] Cl ₂ and hexaammin. There is nickel nitrate [Ni (NH ₃ ) ₆ ] (NO ₃ ) ₂ .

Embodiment 3
In this embodiment, as a second raw material for precipitating a metal by thermal decomposition, the thermal decomposition temperature is higher than that of the complex composed of the above-mentioned inorganic metal compound, but cheaper than the complex, and the oxygen ion constituting the carboxyl group of the carboxylic acid is used. Explain that a carboxylic acid metal compound having both the first characteristic of covalently bonding to a metal ion and the second characteristic of a carboxylic acid consisting of a saturated fatty acid is appropriate. Among the metal carboxylate compounds, the thermal decomposition temperature of the metal carboxylate compound is the lowest at 290 ° C. in the atmospheric atmosphere. On the other hand, the thermal decomposition temperature of the metal octylate compound in the nitrogen atmosphere is 340 ° C., which is 50 ° C. higher than that in the atmospheric atmosphere. Here, the metal is aluminum, and an aluminum carboxylate compound will be described.
Similar to the nickel complex described above, the aluminum compound that precipitates aluminum by thermal decomposition must first disperse in methanol and secondly have these two properties of precipitating aluminum by thermal decomposition.
First, an aluminum compound dispersed in methanol will be described. Aluminum chloride dissolves in water and hydrolyzes to aluminum hydroxide and hydrochloric acid. Also, aluminum hydroxide does not disperse in methanol. Furthermore, aluminum sulfate dissolves in methanol and aluminum ions elute. Also, aluminum oxide does not disperse in methanol. Therefore, these inorganic aluminum compounds having a small molecular weight do not disperse in methanol.
Next, the organoaluminum compound has a property of precipitating aluminum by thermal decomposition. Among the chemical reactions that produce aluminum from organoaluminum compounds, the simplest chemical reaction is the thermal decomposition reaction. That is, aluminum is precipitated only by raising the temperature of the organoaluminum compound. Further, if the organoaluminum compound can be easily synthesized, it can be produced at low cost. An organoaluminum compound having these properties is an aluminum carboxylate compound.
That is, the composition formula of the aluminum carboxylate compound is represented by Al (COOR) ₃ . R is a hydrocarbon, and the composition formula is C _m H _n (where m and n are integers). Among the ions constituting the aluminum carboxylate compound, the aluminum ion Al ³⁺ located in the center of the molecule is the largest. Therefore, when the aluminum ion Al ³⁺ and the oxygen ion O ⁻ constituting the carboxyl group are covalently bonded, the distance between the aluminum ion Al ³⁺ and the oxygen ion O ⁻ is maximized. The reason for this is that the covalent radius of the aluminum ion atom is 121 pm, the covalent radius of the oxygen ion atom is 66 pm, and the covalent radius of the carbon atom is 73 pm. Therefore, in the aluminum carboxylate compound in which the aluminum ion and the oxygen ion constituting the carboxyl group are covalently bonded, the bonding portion between the aluminum ion having the longest bonding distance and the oxygen ion constituting the carboxyl group at the boiling point of the carboxylic acid is formed. It is first split and separated into aluminum and carboxylic acid. When the temperature is further raised, if the carboxylic acid is a saturated fatty acid, the carboxylic acid takes away the heat of vaporization and vaporizes, and aluminum precipitates after the vaporization of the carboxylic acid is completed. Examples of such an aluminum carboxylate compound include aluminum octylate, aluminum laurate, and aluminum stearate. Most of such aluminum carboxylate compounds are inexpensive industrial chemicals commercially available as metal soaps.
Further, if the boiling point of the saturated fatty acid is low, the aluminum carboxylate compound is thermally decomposed at a low temperature, and the heat treatment cost for precipitating aluminum can be reduced. When the hydrocarbon constituting the saturated fatty acid has a long chain structure, the longer the long chain, that is, the larger the molecular weight of the saturated fatty acid, the higher the boiling point of the saturated fatty acid. By the way, the boiling point of lauric acid having a molecular weight of 200.3 at atmospheric pressure is 296 ° C., and the boiling point of stearic acid having a molecular weight of 284.5 at atmospheric pressure is 361 ° C.
Further, when the saturated fatty acid is a saturated fatty acid having a branched chain structure, the chain length is shorter and the boiling point is lower than that of the saturated fatty acid having a linear structure. As a result, the aluminum carboxylate compound composed of saturated fatty acids having a branched chain structure is thermally decomposed at a relatively low temperature. Furthermore, since saturated fatty acids having a branched chain structure have polarity, aluminum carboxylate compounds composed of saturated fatty acids having a branched chain structure also have polarity and are dispersed in a relatively high proportion in polar organic solvents such as methanol. .. Octylic acid is a saturated fatty acid having such a branched structure. The boiling point of octyl acid at atmospheric pressure is 228 ° C, which is 68 ° C lower than that of lauric acid. Therefore, aluminum octylate having a low thermal decomposition temperature is desirable as a raw material for precipitating aluminum. Aluminum octylate is thermally decomposed at 290 ° C. in the air atmosphere to precipitate aluminum, which is dispersed in methanol up to 10% by weight.
Further, the aluminum carboxylate compound is an inexpensive organic aluminum compound that is easy to synthesize. That is, when a carboxylic acid is reacted in a strong alkaline solution such as sodium hydroxide, an alkali metal carboxylate compound is produced. When this alkali metal carboxylate compound is reacted with an inorganic aluminum compound such as aluminum sulfate, an aluminum carboxylate compound is produced.
As described above, aluminum octylate Al (C ₇ H ₁₅ COO) ₃ has a low thermal decomposition temperature and is therefore suitable as a raw material for precipitating aluminum by thermal decomposition.

Example 1
This embodiment is an example in which a graphene junction in which the flat surfaces of graphene are overlapped and bonded is formed on the bottom surface of the container.
First, 2 liters of methanol was filled into a container having a bottom surface of 1.2 m × 1.2 m and a shallow bottom.
Next, a parallel plate electrode having an effective area of 1 m × 1 m in which an electric field is generated in the gap between the two parallel plate electrodes is prepared, and the two parallel plate electrodes are superposed with a gap of 100 μm, and this gap is formed. The graphite particles are evenly squeezed into the parallel. Assuming that the graphite particles are spheres having a particle size of 25 μm and the average thickness of the graphite particles is 10 μm, the graphite particles are evenly packed in the gap of 100 μm formed by the two parallel plate electrodes. In the case, there are 6.4 × 10 ⁷ graphite particles. When a DC voltage of 10.6 kilovolts or more is applied to this group of graphite particles, the interlayer bond between the basal planes of all the graphite particles is broken at the same time. At this time, an aggregate of 1.9 × 10 ¹³ graphenes was obtained, and the aggregate of graphite particles used was only 1.18 g.
Therefore, 5 g of scaly graphite particles (for example, XD100 manufactured by Ito Graphite Industry Co., Ltd.) were stacked and pulled on the surface of a parallel plate electrode having an effective area of an electrode in which an electric field is generated of 1 m × 1 m. This parallel plate electrode was immersed in a container filled with methanol, and the other parallel plate electrode was superposed on the parallel plate electrode, and the two parallel plate electrodes were separated by a gap of 100 μm. A DC voltage of 12 kilovolts was applied between the electrodes. Next, the gap between the two parallel plate electrodes is expanded, the two parallel plate electrodes are tilted in methanol, and vibration acceleration in three directions consisting of 0.2 G is repeatedly applied to the container, and then the container is used. Two parallel plate electrodes were taken out from. As a result, a suspension in which a collection of graphene was precipitated in methanol was produced in the container.
Further, again, vibration acceleration in three directions consisting of 0.2 G was repeatedly applied to the container. Next, the temperature of the container was raised to 65 ° C., and methanol was vaporized. Further, a 1.2 m × 1.2 m aluminum plate is placed on the upper flat surface of the sample formed on the bottom surface of the container, and then a 60 kg weight is placed on the aluminum plate to equalize the upper flat surface of the sample. Compressed to. After removing the weight and the aluminum plate, a vibration acceleration of 0.2 G in three directions was applied to the container, and the sample was taken out from the container. An aluminum plate was placed on the sample taken out again, and a weight of 20 kg was placed on the sample, but the state of the sample did not change.
Next, the two planes and sides of the sample were observed and analyzed using an electron microscope. As the electron microscope, an extremely low accelerating voltage SEM manufactured by JFE Techno Research Co., Ltd. was used. This device can observe the surface with an extremely low accelerating voltage from 100 volts, and has the feature that the surface of the sample can be directly observed without forming a conductive film on the sample. First, the secondary electron beam between 900 and 1000 volts of the backscattered electron beam from the plane of the sample was taken out and image processed. An extremely thin step was confirmed on the flat surface of the sample. Next, the secondary electron beam between 900 and 1000 volts of the backscattered electron beam from the side surface of the sample was taken out and image processing was performed. Five layers of extremely thin substances were stacked. Furthermore, as a result of image processing of the energy of the characteristic X-ray and its intensity, it was confirmed that only carbon atoms were present and the sample was a graphene conjugate in which the flat planes of graphene overlapped with each other. Even if the graphene joint was taken out from the container and a weight of 20 kg was placed on the graphene joint, the graphene joint was not destroyed, so that the flat surfaces of the graphene were joined with a constant joining force. In FIG. 1, a part of the side surface of the graphene junction in which the flat surfaces of graphene overlap each other is enlarged and schematically shown.
Next, the optical performance related to a plurality of parts on the plane of the graphene junction was investigated from the light transmittance and the haze value. The light transmittance in the wavelength region (380-750 nm) of visible light by a spectrophotometer (UV-1280 product of Shimadzu Corporation) was as high as 88-90%. The haze value by the haze meter (Haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd.) was less than 1%. As a result, the graphene conjugate had high transparency.

Example 2
In this embodiment, a transparent conductive base material having a structure in which a graphene bonded body in which flat planes of graphene are overlapped and bonded according to the manufacturing method described in paragraph 10 is thermocompression bonded to a transparent film of synthetic resin is used as a container. This is an example of forming on the bottom surface.
As a transparent film, an acrylic resin transparent film having a film thickness of 50 μm (for example, product number HBS006 of Mitsubishi Rayon Co., Ltd.) was cut into a size of 1.2 m × 1.2 m and placed on the bottom surface of the container. .. After that, a suspension was produced according to the method of Example 1, 10 g of the suspension was filled in a container, and vibration acceleration in three directions consisting of 0.2 G was repeatedly applied to the container. Next, the temperature of the container was raised to 65 ° C., and methanol was vaporized. Further, a 1.2 m × 1.2 m aluminum plate is placed on the upper flat surface of the sample formed on the bottom surface of the container, and then a 60 kg weight is placed on the aluminum plate to equalize the upper flat surface of the sample. Compressed to. After removing the weight and the aluminum plate, a vibration acceleration of 0.2 G in three directions was applied to the container, and the sample was taken out from the container. An aluminum plate was placed on the sample taken out again, and a weight of 20 kg was placed on the sample, but the state of the sample did not change.
Next, the optical performance related to a plurality of parts of the sample was examined from the light transmittance and the haze value as in Example 1. The light transmittance of visible light in the wavelength region (380-750 nm) according to the spectrophotometer had a high value of 86-88%. Moreover, the haze value by the haze meter was less than 2%. As a result, the graphene conjugate had high transparency.

Example 3
This example is an example of forming a transparent electrode made of a collection of nickel fine particles on the transparent conductive base material prepared in Example 2. Hexammine nickel nitrate [Ni (NH ₃ ) ₆ ] (NO ₃ ) ₂ (for example, a product of Mitsuwa Chemical Co., Ltd.) described in paragraph 27 was used as a raw material for the nickel fine particles. As the organic compound, ethylene glycol having a boiling point of 197 ° C., a melting point of -12.6 ° C., a viscosity of 20 ° C. and a viscosity of 21 mPa seconds (for example, a product of Nippon Shokubai Co., Ltd.) described in paragraph 25 was used. ..
First, 29 g (corresponding to 0.1 mol) of hexaammine nickel nitrate is dispersed in methanol so as to be 10% by weight, and then mixed and mixed with this dispersion so that ethylene glycol is 10% by weight. The liquid was prepared. This mixed solution is printed on the surface of the transparent conductive substrate prepared in Example 2 at intervals of 2 mm with a coating film having a width of 3 mm, placed in a heat treatment furnace in an ammonia atmosphere, and heated at 20 ° C./min. The temperature was raised to 210 ° C. at a rate and heat treatment was performed. After that, a 1.2 m × 1.2 m aluminum plate is placed on the upper flat surface of the transparent conductive base material, and a 20 kg weight is placed on the aluminum plate to evenly cover the upper flat surface of the transparent conductive base material. It was compressed to prepare a sample. After removing the weight and the aluminum plate, a vibration acceleration of 0.2 G in three directions was applied to the container, and the sample was taken out from the container.
First, the optical performance at a plurality of parts of the sample on which the coating film was formed was examined from the light transmittance and the haze value as in Example 1. The light transmittance of visible light in the wavelength region according to the spectrophotometer had a high value of 88-90%. Moreover, the haze value by the haze meter was less than 2%. As a result, the portion where the coating film was formed had high transparency.
Next, as a result of measuring the bonding force between the site of the sample on which the coating film was formed and the transparent conductive base material based on the adhesive force test method specified in JIS Z0237, a load of 200 g was withstood. Therefore, the coating film was bonded to the graphene conjugate with a constant bonding force.
In addition, the surface resistance of a plurality of samples on which a coating film was formed was measured with a surface resistance tester (for example, surface resistance tester ST-4 of Simco Japan Co., Ltd.). Since the surface resistance value was 1 × 10 ³ Ω / □, it had a surface resistance close to that of metal.
Further, the surface of the sample on which the coating film was formed was observed with an electron microscope in the same manner as in Example 1. First, with respect to the backscattered electron beam from the surface of the portion where the coating film was formed, the secondary electron beam between 900 and 1000 volts was taken out and image processing was performed. The surface was covered with a collection of granular fine particles with a size of 40-60 nm.
Next, with respect to the reflected electron beam from the surface, the energy between 900 and 1000 volts was extracted and image processing was performed, and the material of the fine particles was analyzed by the shade of the image. No shading was observed in any of the granular fine particles, indicating that the fine particles were composed of a single atom.
Furthermore, the energy of characteristic X-rays from the surface and its intensity were image-processed, and the types of elements constituting the fine particles were analyzed. Since the granular fine particles were composed of only nickel atoms, the granular fine particles are nickel granular fine particles.
From the above results, as a result of heat-treating the coating film of the mixed solution, a collection of nickel granular fine particles is deposited on the transparent conductive base material, and when the plane above the transparent conductive base material is evenly compressed, the nickel fine particles are collected. , Bonded to a transparent conductive substrate with constant strength. In addition, this collection of nickel fine particles showed transparency.

Example 4
This example is an example in which a transparent electrode made of a collection of aluminum fine particles is formed on the transparent conductive base material prepared in Example 2. As the raw material of the aluminum fine particles, aluminum Al (C ₇ H ₁₅ COO) ₃ (for example, a product of Hope Pharmaceutical Co., Ltd.) described in paragraph 28 was used. 46 g (corresponding to 0.1 mol) of aluminum octylate was dispersed in methanol so as to be 10% by weight, and the ethylene glycol used in Example 3 was mixed with this dispersion so as to be 10% by weight. To prepare a mixed solution. This mixed solution was printed on the surface of the transparent conductive substrate prepared in Example 2 at intervals of 2 mm with a coating film having a width of 3 mm, heated to 290 ° C. in the air atmosphere, and left for 1 minute. After that, a 1.2 m × 1.2 m aluminum plate is placed on the upper flat surface of the transparent conductive base material, and a 15 kg weight is placed on the aluminum plate so that the upper flat surface of the transparent conductive base material is evenly placed. It was compressed to prepare a sample. After removing the weight and the aluminum plate, a vibration acceleration of 0.2 G in three directions was applied to the container, and the sample was taken out from the container.
First, as in Example 3, the optical performance at the site of the sample on which the coating film was formed was examined from the light transmittance and the haze value. The light transmittance of visible light in the wavelength region according to the spectrophotometer had a high value of 88-90%. Moreover, the haze value by the haze meter was less than 2%. As a result, the portion where the coating film was formed had high transparency.
Next, as a result of measuring the bonding force between the site of the sample on which the coating film was formed and the transparent conductive substrate based on the adhesive force test method in the same manner as in Example 3, a load of 200 g was withstood. Therefore, the coating film was bonded to the graphene conjugate with a constant bonding force.
In addition, the surface resistance of a plurality of sites of the sample on which the coating film was formed was measured with a surface resistance meter in the same manner as in Example 3. Since the surface resistance value was 1 × 10 ³ Ω / □, it had a surface resistance close to that of metal.
Further, the surface of the sample on which the coating film was formed was observed with an electron microscope in the same manner as in Example 3. The surface was covered with granular aluminum particles consisting of 40-60 nm.
From the above results, as a result of heat-treating the coating film of the mixed solution, a collection of aluminum granular fine particles is deposited on the transparent conductive base material, and when the plane above the transparent conductive base material is evenly compressed, the collection of aluminum fine particles is formed. , Bonded to a transparent conductive substrate with constant strength. In addition, this collection of aluminum fine particles showed transparency.

Claims (5)

A method for producing a transparent conductive base material having a structure in which a graphene junction composed of a collection of graphene obtained by joining the graphene flat surfaces on which the graphene flat surfaces are overlapped is thermocompression bonded to a synthetic resin transparent film is used.
A collection of scaly graphite particles or a collection of massive graphite particles is flatly packed on the surface of one of the two parallel plate electrodes, and the parallel plate electrode is immersed in methanol filled in a container. Further, the other parallel plate electrode is superposed on the one parallel plate electrode, and the two parallel plate electrodes are separated from each other through a collection of the scaly graphite particles or a collection of the massive graphite particles. , The two separated parallel plate electrodes are immersed in the methanol, and then a DC potential difference is applied to the gap between the two parallel plate electrodes, whereby the magnitude of the potential difference is increased to the above 2. An electric field corresponding to the value divided by the size of the gap between the parallel plate electrodes is applied to the collection of scaly graphite particles or the collection of lump graphite particles, and the application of the electric field causes the scaly graphite particles or All of the interlayer bonds of the basal plane forming the massive graphite particles are simultaneously destroyed, and a collection of graphenes corresponding to the basal plane is produced in the gap between the two parallel plate electrodes. The gap between the parallel plate electrodes is expanded, the two parallel plate electrodes are tilted in the methanol, and vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to the container to collect the graphite particles. The two parallel plate electrodes are moved into the methanol through the gap between the two parallel plate electrodes, and then the two parallel plate electrodes are taken out from the container, whereby a collection of the graphite is deposited in the methanol in the container. Graphite is produced,
Next, a transparent film of synthetic resin having the shape of the bottom surface of the container is placed on the bottom surface of the container for producing the transparent conductive base material, and the suspension produced by the above method is further subjected to the transparent conductive base material. The container is filled in an amount required for production, and then vibrations in three directions of front-back, left-right, and up-down are repeatedly applied to the container, whereby a collection of graphenes constituting the suspension is formed. The graphene moves in the methanol constituting the suspension with the flat surface of the graphene facing up, the graphene is diffused throughout the container, and the flat surfaces of the graphene are overlapped with each other via methanol. Is formed on the transparent film of the synthetic resin as the shape of the bottom surface of the container, and then a plate material having the size of the group of graphene is placed on the group of graphene, and further, the container is further placed. Is heated to the boiling point of methanol to vaporize the methanol, and then the plate material is compressed and the container is heated to the Vicat softening temperature of the synthetic resin constituting the transparent film.
As a result, after the methanol is vaporized, a collection of graphenes in which the flat surfaces of the graphenes are overlapped with each other is formed on the transparent film of the synthetic resin as the shape of the bottom surface of the container, and then the graphenes are formed. The collection is compressed, and frictional heat is generated at the portion where the flat surfaces of the graphene overlap each other. The frictional heat causes the flat surfaces of the graphene to join each other, and the flat surfaces of the graphene overlap each other. A graphene joint composed of a collection of the bonded graphenes is formed, the transparent film of the synthetic resin is softened, and the graphene joint is pressure-bonded to the surface of the transparent film of the softened synthetic resin, and the graphene joint is formed. Is heat-bonded to the transparent film of the synthetic resin to form a transparent conductive base material having the shape of the bottom surface on the bottom surface of the container. By repeatedly applying vibration in the direction and taking out the transparent conductive base material from the container, a graphene joint composed of a collection of the graphenes in which the flat surfaces of the graphenes overlap each other is formed of a synthetic resin. This is a method of a transparent conductive base material for producing a transparent conductive base material having a structure in which a transparent film is heat-bonded. The method for forming a transparent electrode on the surface of the transparent conductive base material according to claim 1 is
A metal compound that precipitates a metal having a refractive index of 0.4 or more and 2.4 or less by thermal decomposition in the wavelength region of visible light is dispersed in methanol, and the metal compound is dispersed in the methanol in a molecular state. The first property of dissolving or mixing in the methanol, the second property having a viscosity higher than that of the methanol, the third property having a melting point lower than 20 ° C., and the boiling point are described above. An organic compound having a fourth property lower than the thermal decomposition temperature of the metal compound is mixed with the methanol dispersion to prepare a mixed solution in which the organic compound is uniformly mixed with the methanol dispersion, and the mixture is prepared. The liquid is applied or printed on the surface of the graphene conjugate constituting the transparent conductive base material produced by the production method according to claim 1, and the transparent conductive base material is heat-treated to thermally decompose the metal compound. The first feature is that it is made of a metal having a refractive index of 0.4 or more and 2.4 or less in the visible light wavelength region, and granular fine particles whose particle size is an order of magnitude smaller than that of the visible light wavelength. A collection of metal fine particles having the second characteristic, which is composed of, is deposited all at once on the surface of the graphene junction to which the mixed solution is applied or printed, and the metal fine particles are metal-bonded at a portion where they come into contact with each other. A collection of metal-bonded metal fine particles is formed on the surface of the graphene joint to which the mixed solution is applied or printed, and then the surface of the graphene joint on which the metal fine particles are formed is evenly compressed. The collection of metal-bonded metal fine particles is plastically deformed, and frictional heat is generated at a portion where the plastically deformed collection of metal fine particles comes into contact with the surface of the graphene joint, and the frictional heat causes the plastic deformation. The claim that a collection of metal fine particles is bonded to the surface of the graphene junction, whereby a transparent electrode composed of the collection of metal fine particles is formed on the surface of the graphene junction constituting the transparent conductive substrate. This is a method of forming a transparent electrode on the surface of the transparent conductive base material according to 1. The method for forming a transparent electrode on the surface of the transparent conductive base material according to claim 2 is
The metal compound according to claim 2 thermally decomposes granular fine particles of a metal having both the first characteristic that the metal is nickel or aluminum and the second characteristic that the size of the fine particles is one order of magnitude smaller than the wavelength of visible light. The transparent electrode is formed according to the method of forming a transparent electrode on the surface of the transparent conductive base material according to claim 2, using the metal compound as the metal compound according to claim 2. This is a method of forming a transparent electrode on the surface of the transparent conductive base material according to claim 2. The method for forming a transparent electrode on the surface of the transparent conductive base material according to claim 2 is
The metal compound according to claim 2 is a complex composed of an inorganic metal compound having a metal complex ion in which a ligand composed of an inorganic molecule or an ion is coordinated to a metal ion composed of nickel or aluminum. The organic compound described in 2 is any one kind of organic compound belonging to carboxylic acid esters, glycols or glycol ethers, and the transparent conductive base material according to claim 2 is made by using these two kinds of substances. The method of forming a transparent electrode on the surface of the transparent conductive base material according to claim 2, wherein the transparent electrode is formed according to the method of forming the transparent electrode on the surface. The method for forming a transparent electrode on the surface of the transparent conductive base material according to claim 2 is
The second characteristic of the metal compound according to claim 2 is that the oxygen ion constituting the carboxyl group in the carboxylic acid is covalently bonded to the metal ion composed of nickel or aluminum, and the carboxylic acid is composed of a saturated fatty acid. It is a carboxylic acid metal compound having two characteristics, and the organic compound according to claim 2 is any one kind of organic compound belonging to carboxylic acid esters, glycols or glycol ethers, and these two kinds A transparent electrode is formed on the surface of the transparent conductive base material according to claim 2, according to the method of forming a transparent electrode on the surface of the transparent conductive base material according to claim 2. The method.

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